Mixed p, n-donor ligands, complexes thereof and uses thereof

Abstract

The present invention relates to novel ligands of formula 1, wherein R1 is each substituted or unsubstituted alkyl, perfluoroalkyl, aryl or cycloalkyl; a cyano group; a sulfonyl-SO2-R10 wherein R10 = a C1-C5 alkyl group, a C5-C6 cycloalkyl group, a C5-C10 aryl group, each unsubstituted or substituted by a C1-C4 alkyl group or a C1-C4 perfluoroalkyl group; silyl-Si (R20R30R40), wherein R20, R30 and R40 are, independently of each other, a C1-C6 alkyl group or a C5-C10 aryl group, which are each unsubstituted or substituted by a C1-C4 alkyl group; r2 is each substituted or unsubstituted alkyl, cycloalkyl, adamantyl or aryl; r3, R4 and R5 are each alkyl, cycloalkyl or aryl, which may be unsubstituted or substituted; or at least two of R3, R4 and R5 are alkyl or alkyl ether bridges and form a heterocyclic ring together with the phosphorus atom, or wherein R3 and R6 and / or R4 and R7 and / or R5 and R8 form an alkyl or alkyl ether bridge together with the nitrogen atom to which it is attached form a heterocyclic ring; r6, R7 and R8 are alkyl or aryl, which may be unsubstituted or substituted, or form a heterocyclic ring, alone or together, with R3, R4 or R5 and the nitrogen atom to which it is attached; m, n and o are 0 or 1, with the proviso that at least one of m, n and o is 1, metal complexes thereof and use for catalytic purposes. # imgabs0 #

Description

Background Art

[0001] Many organometallic compounds, especially transition metal and noble metal compounds, are known to be catalysts in chemical synthesis. Many palladium-catalyzed reactions, such as the Heck and Stille reactions, the Hartwig-Buchwald reaction, the Negishi coupling, the Suzuki coupling, and the Sonogashira coupling, are well-established in preparative organic chemistry.

[0002] Nevertheless, there is a constant need for new catalysts that meet specific requirements or have novel properties to expand and complement the scope of preparative chemistry.

[0003] For example, WO 2017 / 093427 shows a palladium-catalyzed selective arylation process.

[0004] WO 2019 / 030304 shows the use of novel ligands for the preparation of metal complexes and their use in organometallic catalysis.

[0005] A new class of nitrogen- and phosphorus-containing ligands has been discovered which surprisingly can form new, previously unknown, catalytically active metal complexes, in particular transition metal compounds.

[0006] These compounds are ligands of formula 1

[0007]

[0008] in

[0009] R1 is independently substituted or unsubstituted alkyl, perfluoroalkyl, aryl or cycloalkyl; cyano; sulfonyl-SO2-R10, wherein R10 = C1-C5 alkyl, C5-C6 cycloalkyl, C5-C10 aryl, each R1 is unsubstituted or substituted by C1-C4 alkyl or C1-C4 perfluoroalkyl; silyl-Si(R20R30R40), wherein R20, R30 and R40 are independently C1-C6 alkyl or C5-C10 aryl, each unsubstituted or substituted by C1-C4 alkyl;

[0010] R2 is independently substituted or unsubstituted alkyl, cycloalkyl, adamantyl or aryl;

[0011] R3, R4 and R5 are each alkyl, cycloalkyl or aryl, which may be unsubstituted or substituted; or at least two of R3, R4 and R5 are alkyl or alkyl ether bridges and together with the phosphorus atom form a heterocyclic ring, or

[0012] wherein R3 and R6 and / or R4 and R7 and / or R5 and R8 together form an alkyl or alkyl ether bridge, which together with the nitrogen atom to which they are attached form a heterocyclic ring;

[0013] R6, R7 and R8 are alkyl or aryl groups which may be unsubstituted or substituted, or individually or collectively form a heterocyclic ring with R3, R4 or R5 and the nitrogen atom to which they are attached;

[0014] m, n and o are 0 or 1, provided that at least one of m, n and o is 1.

[0015] The present invention also relates to metal complexes, in particular transition metal and noble metal complexes, comprising at least one ligand of formula 1.

[0016] The present invention also relates to a method for carrying out coupling reactions involving such complexes, which can be isolated before use in coupling reactions or can be used in a one-pot reaction without isolating such complexes.

[0017] As shown in the examples, the corresponding ligands of the present invention and complexes containing such ligands are able to effectively carry out coupling reactions. Nitrogen substitution leads to significant differences that are not always predictable, but the behavior of the ligands is very different from their alkyl / aryl analogs:

[0018] 1) Structural aspects / stability The introduction of nitrogen allows the ligands of Formula 1 to react primarily as P,N ligands, rather than just as simple monophosphanes. Some complexes exhibit N-coordination, which would be impossible without nitrogen. This N-coordination naturally also affects reactivity, resulting in Pd(0)dba complexes with ligands of Formula 1 being significantly more stable.

[0019] 2) Range of variation Due to the greater range of aminophosphanes readily prepared from PCl3 and simple amines, it is easier to generate a wider range of ligands of formula 1 than with alkyl and aryl substituents. This makes it easier to control the steric properties and binding capacity of the nitrogen.

[0020] 3) Reactivity As mentioned above, the behavior of ligands of formula 1 is significantly different from their alkyl / aryl analogs. Therefore, in many applications, they may be less active because the complex is more stable. However, there are also advantages in cases where additional coordination is required. The best example to date is the monoarylation of acetone, which showed only very poor selectivity when using the YPhos ligand described in WO 2019 / 030304. However, with ligands of formula 1, excellent selectivity and yield are possible, and one of the catalysts is the best catalyst for this reaction described in the literature to date. Summary of the Invention

[0021] 1. A ligand of formula 1,

[0022]

[0023] wherein R1 is independently substituted or unsubstituted alkyl, perfluoroalkyl, aryl or cycloalkyl; cyano; sulfonyl-SO2-R10, wherein R10 = C1-C5 alkyl, C5-C6 cycloalkyl, C5-C10 aryl, each unsubstituted or substituted by C1-C4 alkyl or C1-C4 perfluoroalkyl; silyl-Si(R20R30R40), wherein R20, R30 and R40 are independently C1-C6 alkyl or C5-C10 aryl, each unsubstituted or substituted by C1-C4 alkyl;

[0024] R2 is independently substituted or unsubstituted alkyl, cycloalkyl, adamantyl or aryl;

[0025] R3, R4 and R5 are each alkyl, cycloalkyl or aryl, which may be unsubstituted or substituted; or at least two of R3, R4 and R5 are alkyl or alkyl ether bridges and together with the phosphorus atom form a heterocyclic ring, or

[0026] wherein R3 and R6 and / or R4 and R7 and / or R5 and R8 together form an alkyl or alkyl ether bridge, which together with the nitrogen atom to which they are attached form a heterocyclic ring;

[0027] R6, R7 and R8 are alkyl or aryl groups which may be unsubstituted or substituted, or individually or collectively form a heterocyclic ring with R3, R4 or R5 and the nitrogen atom to which they are attached;

[0028] m, n and o are 0 or 1, provided that at least one of m, n and o is 1.

[0029] 2. A ligand according to item 1, wherein R1 is selected from C1 to C9 alkyl; C4-C8 cycloalkyl; C5-C10 aryl; cyano; sulfonyl-SO2-R10, wherein R10 = C1-C5 alkyl, C5-C6 cycloalkyl, C5-C10 aryl, each of which is unsubstituted or substituted with one or more C1 to C4 alkyl, C1 to C4 alkoxy or C1 to C4 perfluoroalkyl; silyl-Si(R20R30R40), wherein each of R20, R30 and R40 is independently C1-C6 alkyl or C5-C10 aryl, each of which is unsubstituted or substituted with C1-C4 alkyl, or R1 is C5-C10 aryl, which may be substituted one or more times with C1 to C5 alkyl, C1 to C5 alkoxy or C1 to C5 perfluoroalkyl.

[0030] 3. The ligand according to any of the preceding clauses, wherein R2 is C1 to C9 alkyl, C4-C8 cycloalkyl, adamantyl, C5 to C10 aryl, which may be unsubstituted or substituted with one or more C1 to C5 alkyl, C1 to C5 alkoxy or C1 to C5 perfluoroalkyl.

[0031] 4. A ligand according to any of the preceding clauses, wherein R3, R4 and R5 are independently C1 to C9 alkyl, C4-C8 cycloalkyl, adamantyl, C5 to C10 aryl, which may be unsubstituted or substituted by C1 to C5 alkyl, C1 to C5 alkoxy or C1 to C5 perfluoroalkyl; or at least two of R3, R4 and R5 are C2 to C10 alkyl, C2 to C10 alkenyl or C2 to C10 alkyl ether bridge and, together with the phosphorus atom, form a heterocycle.

[0032] 5. A ligand according to any of the preceding clauses, wherein R3, R4 and R5 are independently C1 to C5 alkyl, C4-C8 cycloalkyl, adamantyl, C5 to C6 aryl, which may be unsubstituted or substituted by C1 to C5 alkyl, C1 to C5 alkoxy or C1 to C5 perfluoroalkyl; or at least two of R3, R4 and R5 are C2 to C5 alkyl, C2 to C5 alkenyl or C2 to C4 alkyl ether bridge and, together with the phosphorus atom, form a heterocycle.

[0033] 6. A ligand according to any of the preceding clauses, wherein at least two of R3, R4 and R5 together are C2 to C8 alkyl or a C2 to C8 alkyl ether bridge, which is optionally substituted with one or more C1 to C5 alkyl or cycloalkyl groups; or the C2 to C8 alkyl or C2 to C8 alkyl ether bridge is part of a fused C4 to C8 cycloalkyl ring, forming a heterocycle with the phosphorus atom.

[0034] 7. A ligand according to any of the preceding clauses, wherein R6, R7 and R8 are C1 to C9 alkyl or C5 to C10 aryl, which may be unsubstituted or substituted by one or more C1 to C5 alkyl, C1 to C5 alkoxy or C1 to C5 perfluoroalkyl; or form a heterocycle individually or collectively with R3, R4 or R5 and the nitrogen atom to which they are attached.

[0035] 8. A ligand according to any of the preceding clauses, wherein R3 and R6 and / or R4 and R7 and / or R5 and R8 together are C2 to C8 alkyl or a C2 to C8 alkyl ether bridge, which is optionally substituted with one or more C1 to C5 groups, or the C2 to C8 alkyl or C2 to C8 alkyl ether bridge is part of a fused C4 to C8 cycloalkyl ring, together with the nitrogen atom to which it is attached, to form a heterocycle.

[0036] 9. The ligand according to any of the preceding clauses, wherein R1 represents C1 to C9 alkyl, C4-C8 cycloalkyl, C5-C10 aryl, which may be unsubstituted or substituted by C1 to C5 alkyl, C1 to C5 alkoxy or C1 to C5 perfluoroalkyl.

[0037] 10. A ligand according to any of the preceding clauses, wherein R1 is selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-pentyl (pentyl), 2-pentyl (sec-pentyl), 3-pentyl, 2-methylbutyl, 3-methylbutyl (iso-pentyl / iso-amyl), 3-methylbutan-2-yl, 2-methylbutan-2-yl, 2,2-dimethylpropyl (neopentyl), n-hexyl, trifluoromethyl, cyclobutyl, cyclopentyl, cyclohexyl, menthyl, phenyl, o-toluoyl, naphthyl, o-methoxyphenyl, o-ethoxyphenyl, di-(o-methoxy)phenyl, p-trifluoromethylphenyl, trimethylsilyl, triisopropyl-silyl, tri-tert-butylsilyl, cyano, methylsulfonyl, toluoylsulfonyl and trifluoromethylsulfonyl.

[0038] 11. A ligand according to any of the preceding clauses, wherein R2 is selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-pentyl (pentyl), 2-pentyl (sec-pentyl), 3-pentyl, 2-methylbutyl, 3-methylbutyl (isopentyl), 3-methylbutan-2-yl, 2-methylbutan-2-yl, 2,2-dimethylpropyl (neopentyl), n-hexyl, trifluoromethyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, phenyl, o-methylphenyl, m-methylphenyl or p-methylphenyl, naphthyl.

[0039] 12. A ligand according to any of the preceding clauses, wherein R3, R4, R5, R6, R7 and R8 are independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentylbutyl, n-pentyl, n-pentyl (pentyl), 2-pentyl (sec-pentyl), 3-pentyl, 2-methylbutyl, 3-methylbutyl (isopentyl), 3-methylbutan-2-yl, 2-methylbutan-2-yl, 2,2-dimethylpropyl (neopentyl), n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, mesityl.

[0040] 13. The ligand according to any of the preceding clauses, wherein at least two or at least one of m, n and o is 1.

[0041] 14. The ligand according to any of the preceding clauses, wherein all of m, n and o are 1.

[0042] 15. A ligand according to any one of the preceding clauses, wherein

[0043] R1 is C1 to C9 alkyl, C5-C10 aryl, each unsubstituted or substituted by C1 to C4 alkyl; sulfonyl-SO2-R10, wherein R10 = C5-C10 aryl, each unsubstituted or substituted by C1 to C4 alkyl;

[0044] R2 is C1 to C9 alkyl, C4 to C8 cycloalkyl or adamantyl;

[0045] R3, R4 and R5 are independently C1 to C9 alkyl, C4 to C8 cycloalkyl, adamantyl, C5 to C10 aryl; R6, R7 and R8 are C1 to C9 alkyl or C5 to C10 aryl, which may be unsubstituted or substituted with one or more C1 to C5 alkyl groups; and / or wherein

[0046] R3 and R6 and / or R4 and R7 and / or R5 and R8 together are C2 to C8 alkyl or a C2 to C8 alkyl ether bridge, optionally the C2 to C8 alkyl bridge may be partly or fully part of a fused C4 to C8 cycloalkyl ring.

[0047] 16. A ligand according to any one of the preceding clauses, wherein

[0048] R1 is C1 to C9 alkyl, C5-C10 aryl, each unsubstituted or substituted by C1 to C4 alkyl; sulfonyl-SO2-R10, wherein R10 = C5-C10 aryl, each unsubstituted or substituted by C1 to C4 alkyl;

[0049] R2 is C1 to C9 alkyl, C4 to C8 cycloalkyl or adamantyl;

[0050] At least two of m, n and o are 1;

[0051] At least two of R3, R4 and R5 together are C2 to C8 alkyl or C2 to C8 alkyl ether bridge, which is optionally substituted with one or more C1 to C5 alkyl or cycloalkyl groups; or the C2 to C8 alkyl or C2 to C8 alkyl ether bridge is part of a fused C4 to C8 cycloalkyl ring, forming a heterocyclic ring with the phosphorus atom;

[0052] R6, R7 and / or R8 are C1 to C6 alkyl or C5-C10 aryl, which are unsubstituted or substituted with one or more C1 to C5 alkyl groups;

[0053] Provided that if one of R3, R4 and R5 is not a C2-C8 alkyl bridge or a C2-C8 alkyl ether bridge, then it is a C4-C8 cycloalkyl or adamantyl group.

[0054] 17. A ligand according to any one of the preceding clauses, wherein

[0055] R1 is C1 to C9 alkyl, C5-C10 aryl, each unsubstituted or substituted by C1 to C4 alkyl; sulfonyl-SO2-R10, wherein R10 = C5-C10 aryl, each unsubstituted or substituted by C1 to C4 alkyl;

[0056] R2 is C1 to C9 alkyl, C4 to C8 cycloalkyl or adamantyl;

[0057] R3, R4 and R5 are independently C1 to C9 alkyl, C4 to C8 cycloalkyl, adamantyl, C5 to C10 aryl; R6, R7 and R8 are C1 to C9 alkyl or C5 to C10 aryl, which may be unsubstituted or substituted with one or more C1 to C5 alkyl groups; and / or wherein

[0058] R3 and R6 and / or R4 and R7 and / or R5 and R8 together are C2 to C8 alkyl or a C2 to C8 alkyl ether bridge, optionally the C2 to C8 alkyl bridge may be partly or fully part of a fused C4 to C8 cycloalkyl ring.

[0059] 18. A ligand according to any one of the preceding clauses, wherein

[0060] R1 is C1 to C9 alkyl or C5-C10 aryl, each unsubstituted or substituted with one or more C1 to C4 alkyl groups;

[0061] R2 is C1 to C9 alkyl, C4 to C8 cycloalkyl or adamantyl;

[0062] m is 0, n and o are 1;

[0063] R3 is C4-C8 cycloalkyl or adamantyl;

[0064] R4 and R5 together are C2 to C8 alkyl or C2 to C8 alkyl ether bridges forming a heterocyclic ring with the phosphorus atom, said C2 to C8 alkyl or C2 to C8 alkyl ether bridge being optionally substituted with one or more C1 to C5 alkyl groups; or said C2 to C8 alkyl or C2 to C8 alkyl ether bridge is part of a fused C4 to C8 cycloalkyl ring in whole or in part;

[0065] R7 and R8 are C1 to C9 alkyl or C5 to C10 aryl, which may be unsubstituted or substituted with one or more C1 to C5 alkyl groups.

[0066] 19. A ligand according to any one of the preceding clauses, wherein

[0067] R1 is C1 to C9 alkyl or C5-C10 aryl, each unsubstituted or substituted with one or more C1 to C4 alkyl groups;

[0068] R2 is C1 to C9 alkyl, C4 to C8 cycloalkyl or adamantyl;

[0069] m, n, and o are 1; and

[0070] R3, R4 and R5 are independently C1 to C9 alkyl, C4 to C8 cycloalkyl or C5 to C10 aryl; R6, R7 and R8 are C1 to C9 alkyl or C5 to C10 aryl, which may be unsubstituted or substituted with one or more C1 to C5 alkyl groups.

[0071] 20. A ligand according to any one of the preceding clauses, wherein

[0072] R1 is C1 to C9 alkyl or C5-C10 aryl, each unsubstituted or substituted with one or more C1 to C4 alkyl groups;

[0073] R2 is C1 to C9 alkyl, C4 to C8 cycloalkyl or adamantyl;

[0074] m, n, and o are 1; and

[0075] Each pair of R3 and R6, R4 and R7, R5 and R8 together is a C2 to C8 alkyl bridge or a C2 to C8 alkyl ether bridge, optionally the C2 to C8 alkyl bridge may be part of a fused C4 to C8 cycloalkyl ring in part or in whole.

[0076] 21. The ligand according to any of the preceding clauses, wherein R1 is selected from methyl, isopropyl, phenyl, o-tolyl.

[0077] 22. The ligand according to any of the preceding clauses, wherein R2 is selected from methyl, isopropyl, tert-butyl, cyclohexyl, phenyl and adamantyl.

[0078] 23. The ligand according to any of the preceding clauses, wherein R3, R4 and R5 are methyl, phenyl, mesityl.

[0079] 24. The ligand according to any of the preceding clauses, wherein one or more of R6, R7 and R8 is methyl, isopropyl, isopentyl, neopentyl, phenyl, mesityl.

[0080] 25. A ligand according to any of the preceding clauses, wherein R3 and R6 and / or R4 and R7 and / or R5 and R8 together with the nitrogen atom to which they are attached form a piperidinyl or morpholinyl ring.

[0081] 26. A ligand according to any of the preceding clauses, wherein R3 and R6 and R4 and R7 and R5 and R8 together with the nitrogen atom to which they are attached form a piperidinyl or morpholinyl ring.

[0082] 27. A metal complex comprising a transition metal and a ligand according to any one of items 1 to 26, and optionally comprising at least one organic ligand L and / or at least one halogen X.

[0083] 28. The metal complex according to Item 27, wherein the transition metal is a noble metal.

[0084] 29. The metal complex according to item 27 or 28, wherein the transition metal is selected from the group consisting of ruthenium, osmium, rhodium, iridium, palladium, platinum, silver and gold, in particular selected from the group consisting of rhodium, iridium, palladium and gold.

[0085] 30. The metal complex according to any one of clauses 27 to 29, wherein the organic ligand is selected from the group consisting of dibenzylideneacetone (DBA), acetylacetone (acac), p-tolyl, m-tolyl, o-tolyl, cyclooctadiene (COD) and carbon monoxide.

[0086] 31. The metal complex according to any one of clauses 27 to 30, wherein the halogen is chlorine or bromine.

[0087] 32. A method for performing a coupling reaction, comprising the steps of:

[0088] - providing a reaction mixture comprising at least a substrate, a coupling partner and a metal complex comprising a ligand according to any one of clauses 1 to 26; and

[0089] - reacting the substrate with the coupling partner in the presence of the metal complex or a derivative thereof to form a coupling product.

[0090] 33. A method of performing a coupling reaction according to claim 32, wherein the metal complex comprising a ligand is a metal complex according to any one of clauses 27 to 31.

[0091] 34. The process according to one or more of clauses 32 or 33, wherein the substrate is a substituted aromatic compound.

[0092] 35. The method according to clause 34, wherein the substituted aromatic compound is an aromatic or heteroaromatic compound.

[0093] 36. The method according to clause 34 or 35, wherein the substituted aromatic compound is substituted with a leaving group and / or an unsaturated aliphatic group or a leaving group.

[0094] 37. The method according to clause 36, wherein the leaving group is selected from the group consisting of halogen, triflate, tosylate, norsulfonate and mesylate, and / or the unsaturated aliphatic group is selected from the group consisting of olefins or alkynes, in particular having 2 to 12 carbon atoms, in particular having 2 to 8 carbon atoms.

[0095] 38. The process according to one or more of the preceding clauses, wherein the coupling partner is an organometallic compound.

[0096] 39. The method of clause 38, wherein the organometallic compound is selected from the group consisting of organoboron compounds, organolithium compounds, organozinc compounds, organolithium compounds, organosodium compounds, organopotassium compounds, and Grignard's compounds.

[0097] 40. The method according to clause 38 or 39, wherein the organometallic compound contains at least one aromatic group.

[0098] 41. The method according to clause 38 or 39, wherein the organometallic compound contains at least one unsaturated aliphatic group.

[0099] 42. The method according to clause 38 or 39, wherein the organometallic compound contains at least one saturated aliphatic group.

[0100] 43. The method according to one or more of clauses 32 to 42, wherein the coupling reaction can be selected from the group consisting of:

[0101] (i) Catalytic hydrofunctionalization of alkynes and alkenes;

[0102] (ii) Catalytic hydroamination of alkynes and alkenes;

[0103] (iii) catalytic OH addition reactions of alkynes and alkenes;

[0104] (iv) catalyzing coupling reactions;

[0105] (v) catalyzed Kumada coupling reaction, Murahashi coupling reaction, Negishi coupling reaction or Suzuki coupling reaction, especially for the production of biarylene;

[0106] (vi) catalyzing cross-coupling reactions, in particular CN and CO coupling reactions; and / or

[0107] (vii) Catalysis of Heck coupling reactions, particularly for the preparation of arylated alkenes, and Sonogashira coupling reactions, particularly for the preparation of arylated and olefinated alkynes.

[0108] (vii) Catalytic α-arylation of carbonyl compounds and imines. DETAILED DESCRIPTION

[0109] The present invention relates to a ligand of formula 1,

[0110]

[0111] wherein R1 is independently substituted or unsubstituted alkyl, perfluoroalkyl, aryl or cycloalkyl; cyano; sulfonyl-SO2-R10, wherein R10 = C1-C5 alkyl, C5-C6 cycloalkyl, C5-C10 aryl, each unsubstituted or substituted by C1-C4 alkyl or C1-C4 perfluoroalkyl; silyl-Si(R20R30R40), wherein R20, R30 and R40 are independently C1-C6 alkyl or C5-C10 aryl, each unsubstituted or substituted by C1-C4 alkyl;

[0112] R2 is independently substituted or unsubstituted alkyl, cycloalkyl, adamantyl or aryl;

[0113] R3, R4 and R5 are each alkyl, cycloalkyl or aryl, which may be unsubstituted or substituted; or at least two of R3, R4 and R5 are alkyl or alkyl ether bridges and together with the phosphorus atom form a heterocyclic ring, or

[0114] wherein R3 and R6 and / or R4 and R7 and / or R5 and R8 together form an alkyl or alkyl ether bridge, which together with the nitrogen atom to which they are attached form a heterocyclic ring;

[0115] R6, R7 and R8 are alkyl or aryl groups which may be unsubstituted or substituted, or form a heterocyclic ring individually or collectively with R3, R4 or R5 and the nitrogen atom to which they are attached; and m, n and o are 0 or 1, provided that at least one of m, n and o is 1.

[0116] In general, in the ligand of Formula 1, R1 is selected from C1 to C9 alkyl; C4-C8 cycloalkyl; C5-C10 aryl; cyano; sulfonyl-SO2-R10, wherein R10 = C1-C5 alkyl, C5-C6 cycloalkyl, C5-C10 aryl, each of which is unsubstituted or substituted with one or more C1 to C4 alkyl, C1 to C4 alkoxy or C1 to C4 perfluoroalkyl; silyl-Si(R20R30R40), wherein each of R20, R30 and R40 is independently C1-C6 alkyl or C5-C10 aryl, each of which is unsubstituted or substituted with C1-C4 alkyl, or R1 is C5-C10 aryl, which may be substituted one or more times with C1 to C5 alkyl, C1 to C5 alkoxy or C1 to C5 perfluoroalkyl.

[0117] In a specific embodiment, R1 represents a C1 to C9 alkyl group, a C4-C8 cycloalkyl group, or a C5-C10 aryl group, and the aryl group may be unsubstituted or substituted by a C1 to C5 alkyl group, a C1 to C5 alkoxy group, or a C1 to C5 perfluoroalkyl group.

[0118] More specifically, R1 is selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-pentyl (pentyl), 2-pentyl (sec-pentyl), 3-pentyl, 2-methylbutyl, 3-methylbutyl (isopentyl), 3-methylbut-2-yl, 2-methylbut-2-yl, 2,2-dimethylpropyl (neopentyl), n-hexyl, trifluoromethyl, cyclobutyl, cyclopentyl, cyclohexyl, menthyl, phenyl, o-toluoyl, naphthyl, o-methoxyphenyl, o-ethoxyphenyl, di-(o-methoxy)phenyl, p-trifluoromethylphenyl, trimethylsilyl, triisopropyl-silyl, tri-tert-butylsilyl, cyano, methylsulfonyl, toluoylsulfonyl and trifluoromethylsulfonyl.

[0119] Additionally, in the ligand of formula 1, R2 is typically a C1 to C9 alkyl group, a C4-C8 cycloalkyl group, an adamantyl group, a C5 to C10 aryl group, which may be unsubstituted or substituted with one or more C1 to C5 alkyl groups, C1 to C5 alkoxy groups, or C1 to C5 perfluoroalkyl groups.

[0120] More specifically, R2 is selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-pentyl (pentyl), 2-pentyl (sec-pentyl), 3-pentyl, 2-methylbutyl, 3-methylbutyl (isopentyl), 3-methylbutan-2-yl, 2-methylbutan-2-yl, 2,2-dimethylpropyl (neopentyl), n-hexyl, trifluoromethyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, phenyl, o-methylphenyl, m-methylphenyl or p-methylphenyl, naphthyl.

[0121] R3, R4 and R5 are independently C1-C9 alkyl, C4-C8 cycloalkyl, adamantyl, 1-adamantyl, 2-adamantyl, C5-C10 aryl, which may be unsubstituted or substituted with C1-C5 alkyl, C1-C5 alkoxy or C1-C5 perfluoroalkyl. In an alternative embodiment, at least two of R3, R4 and R5 are C2 to C10 alkyl, C2 to C10 alkenyl or C2 to C10 alkyl ether bridges and together with the phosphorus atom form a heterocycle.

[0122] This means, for example, that when m is 0 (zero), R3 can be a methyl or cyclohexyl ring directly attached to the phosphorus atom, R4 and R5 together can be a C2 alkenyl bridge or a C3 alkyl bridge, and in the case where n and o are 1, a five-membered unsaturated ring consisting of P and two substituted nitrogen atoms, both attached to a C2 alkenyl bridge, or a six-membered saturated ring consisting of P and two substituted nitrogen atoms, both attached to a C3 alkyl bridge, will be formed.

[0123] More specifically, R3, R4 and R5 are independently C1 to C5 alkyl, C4-C8 cycloalkyl, adamantyl, 1-adamantyl, 2-adamantyl, C5 to C6 aryl, which may be unsubstituted or substituted by C1 to C5 alkyl, C1 to C5 alkoxy or C1 to C5 perfluoroalkyl; or at least two of R3, R4 and R5 are C2 to C5 alkyl, C2 to C5 alkenyl or C2 to C4 alkyl ether bridge, and together with the phosphorus atom form a heterocycle.

[0124] In another embodiment, at least two of R3, R4 and R5 together are C2 to C8 alkyl or C2 to C8 alkyl ether bridge, which is optionally substituted with one or more C1 to C5 alkyl or cycloalkyl groups; or the C2 to C8 alkyl or C2 to C8 alkyl ether bridge is part of a fused C4 to C8 cycloalkyl ring, forming a heterocycle with the phosphorus atom.

[0125] This means, for example, that when m is 0 (zero), R3 can be a methyl or cyclohexyl ring directly attached to the phosphorus atom, R4 and R5 together can be a 1,2-cyclohexyl bridge, and in the case where n and o are 1, a five-membered unsaturated ring will be formed consisting of P, two substituted nitrogen atoms, each attached to the 1-position and the 2-position of the cyclohexyl ring, providing a C2 alkyl bridge, such that the heterocyclic five-membered ring is fused to the cyclohexyl ring.

[0126] In another embodiment, R6, R7 and R8 are independently C1 to C9 alkyl or C5 to C10 aryl, which may be unsubstituted or substituted with one or more C1 to C5 alkyl, C1 to C5 alkoxy or C1 to C5 perfluoroalkyl; or R6, R7 and R8, alone or in combination, form a heterocycle with R3, R4 or R5 and the nitrogen atom to which they are attached. This means that at least one

[0127] In yet another embodiment, R3 and R6 and / or R4 and R7 and / or R5 and R8 together are C2 to C8 alkyl or C2 to C8 alkyl ether bridge, which is optionally substituted with one or more C1 to C5 groups, or said C2 to C8 alkyl or C2 to C8 alkyl ether bridge is part of a fused C4 to C8 cycloalkyl ring, together with the nitrogen atom to which it is attached, to form a heterocycle.

[0128] This means that in this embodiment, at least one of m, n and o is 1, and at least one of R3, R4 or R7 is also linked to the nitrogen atom to which it is linked via the respective remaining R6, R7 and R8 linked to the same nitrogen atom so as to form an aliphatic ring with the nitrogen atom, optionally containing one or more oxygen atoms as ring members.

[0129] Specifically, R3 and R6 can form together, for example, an aziridine ring, a pyrrolidine ring or a piperidine ring, or, in the case of an alkyl ether bridge, for example, an oxaziridine ring, an oxazolidine ring, an isoxazolidine ring or a morpholine ring. The same is possible for two or all of R4 and R7, R5 and R8, or R3 and R6, R4 and R7 and R5 and R8.

[0130] In another embodiment, R3, R4, R5, R6, R7 and R8 are independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentylbutyl, n-pentyl, n-pentyl (pentyl), 2-pentyl (sec-pentyl), 3-pentyl, 2-methylbutyl, 3-methylbutyl (isopentyl), 3-methylbutan-2-yl, 2-methylbutan-2-yl, 2,2-dimethylpropyl (neopentyl), n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, mesityl.

[0131] In all of the aforementioned embodiments, at least one of m, n, and o must be 1. For all ligands in any of the aforementioned embodiments, at least two of m, n, and o may be 1.

[0132] In some embodiments, it is possible for the ligand to have all of m, n, and o to be 1.

[0133] Another embodiment relates to a ligand wherein

[0134] R1 is C1 to C9 alkyl, C5-C10 aryl, each unsubstituted or substituted by C1 to C4 alkyl; sulfonyl-SO2-R10, wherein R10 = C5-C10 aryl, each unsubstituted or substituted by C1 to C4 alkyl;

[0135] R2 is a C1 to C9 alkyl group, a C4 to C8 cycloalkyl group or an adamantyl group, which may be a 1-adamantyl group or a 2-adamantyl group;

[0136] R3, R4 and R5 are independently C1 to C9 alkyl, C4 to C8 cycloalkyl, adamantyl, C5 to C10 aryl; R6, R7 and R8 are C1 to C9 alkyl or C5 to C10 aryl, which may be unsubstituted or substituted with one or more C1 to C5 alkyl groups; and / or wherein

[0137] R3 and R6 and / or R4 and R7 and / or R5 and R8 together are C2 to C8 alkyl or a C2 to C8 alkyl ether bridge, optionally the C2 to C8 alkyl bridge may be partly or fully part of a fused C4 to C8 cycloalkyl ring.

[0138] Yet another embodiment relates to a ligand wherein

[0139] R1 is C1 to C9 alkyl, C5-C10 aryl, each unsubstituted or substituted by C1 to C4 alkyl; sulfonyl-SO2-R10, wherein R10 = C5-C10 aryl, each unsubstituted or substituted by C1 to C4 alkyl;

[0140] R2 is a C1 to C9 alkyl group, a C4 to C8 cycloalkyl group or an adamantyl group, which may be a 1-adamantyl group or a 2-adamantyl group;

[0141] At least two of m, n and o are 1;

[0142] At least two of R3, R4 or R5 together are C2 to C8 alkyl or C2 to C8 alkyl ether bridge, which is optionally substituted with one or more C1 to C5 alkyl or cycloalkyl groups; or the C2 to C8 alkyl or C2 to C8 alkyl ether bridge is part of a fused C4 to C8 cycloalkyl ring, forming a heterocyclic ring with the phosphorus atom;

[0143] R6, R7 and / or R8 are C1 to C6 alkyl or C5-C10 aryl, which are unsubstituted or substituted with one or more C1 to C5 alkyl groups;

[0144] Provided that if one of R3, R4 and R5 is not a C2-C8 alkyl bridge or a C2-C8 alkyl ether bridge, it is a C4-C8 cycloalkyl or adamantyl group, which may be 1-adamantyl or 2-adamantyl.

[0145] Another embodiment relates to a ligand wherein

[0146] R1 is C1 to C9 alkyl, C5-C10 aryl, each unsubstituted or substituted by C1 to C4 alkyl; sulfonyl-SO2-R10, wherein R10 = C5-C10 aryl, each unsubstituted or substituted by C1 to C4 alkyl;

[0147] R2 is a C1 to C9 alkyl group, a C4 to C8 cycloalkyl group or an adamantyl group, which may be a 1-adamantyl group or a 2-adamantyl group;

[0148] R3, R4 and R5 are independently C1 to C9 alkyl, C4 to C8 cycloalkyl, adamantyl which may be 1-adamantyl or 2-adamantyl, C5 to C10 aryl; R6, R7 and R8 are C1 to C9 alkyl or C5 to C10 aryl, which may be unsubstituted or substituted with one or more C1 to C5 alkyl groups; and / or wherein

[0149] R3 and R6 and / or R4 and R7 and / or R5 and R8 together are C2 to C8 alkyl or a C2 to C8 alkyl ether bridge, optionally the C2 to C8 alkyl bridge may be partly or fully part of a fused C4 to C8 cycloalkyl ring.

[0150] Yet another embodiment relates to a ligand wherein

[0151] R1 is C1 to C9 alkyl or C5-C10 aryl, each unsubstituted or substituted with one or more C1 to C4 alkyl groups;

[0152] R2 is a C1 to C9 alkyl group, a C4 to C8 cycloalkyl group or an adamantyl group, which may be a 1-adamantyl group or a 2-adamantyl group;

[0153] m is 0, n and o are 1;

[0154] R3 is a C4 to C8 cycloalkyl group or adamantyl group, which may be 1-adamantyl or 2-adamantyl;

[0155] R4 and R5 together are C2 to C8 alkyl or C2 to C8 alkyl ether bridges forming a heterocyclic ring with the phosphorus atom, said C2 to C8 alkyl or C2 to C8 alkyl ether bridge being optionally substituted with one or more C1 to C5 alkyl groups; or said C2 to C8 alkyl or C2 to C8 alkyl ether bridge is part of a fused C4 to C8 cycloalkyl ring in whole or in part;

[0156] R7 and R8 are C1 to C9 alkyl or C5 to C10 aryl, which may be unsubstituted or substituted with one or more C1 to C5 alkyl groups.

[0157] Another embodiment relates to a ligand wherein

[0158] R1 is C1 to C9 alkyl or C5-C10 aryl, each unsubstituted or substituted with one or more C1 to C4 alkyl groups;

[0159] R2 is a C1 to C9 alkyl group, a C4 to C8 cycloalkyl group or an adamantyl group, which may be a 1-adamantyl group or a 2-adamantyl group;

[0160] m, n, and o are 1; and

[0161] R3, R4 and R5 are independently C1 to C9 alkyl, C4 to C8 cycloalkyl or C5 to C10 aryl; R6, R7 and R8 are C1 to C9 alkyl or C5 to C10 aryl, which may be unsubstituted or substituted with one or more C1 to C5 alkyl groups.

[0162] In another embodiment, the ligand contains a substituent

[0163] R1 is C1 to C9 alkyl or C5-C10 aryl, each unsubstituted or substituted with one or more C1 to C4 alkyl groups;

[0164] R2 is a C1 to C9 alkyl group, a C4 to C8 cycloalkyl group or an adamantyl group, which may be a 1-adamantyl group or a 2-adamantyl group;

[0165] m, n, and o are 1; and

[0166] Each pair of R3 and R6, R4 and R7, R5 and R8 together is a C2 to C8 alkyl bridge or a C2 to C8 alkyl ether bridge, optionally the C2 to C8 alkyl bridge may be part of a fused C4 to C8 cycloalkyl ring in part or in whole.

[0167] Specifically, R1 is selected from methyl, isopropyl, phenyl and o-tolyl.

[0168] Specifically, R2 is selected from methyl, isopropyl, tert-butyl, cyclohexyl, phenyl and adamantyl, which may be 1-adamantyl or 2-adamantyl.

[0169] Specifically, R3, R4 and R5 are selected from methyl, phenyl and mesityl.

[0170] Specifically, one or more of R6, R7 and R8 are methyl, isopropyl, isopentyl, neopentyl, phenyl, mesityl.

[0171] Specifically, in the ligand according to any one of the preceding embodiments, R3 and R6 and / or R4 and R7 and / or R5 and R8 together with the nitrogen atom to which they are attached form a piperidinyl or morpholinyl ring.

[0172] A ligand according to any of the preceding clauses, wherein R3 and R6 and R4 and R7 and R5 and R8 together with the nitrogen atom to which they are attached form a piperidinyl or morpholinyl ring, and therefore, all of m, n and o are equal to 1.

[0173] The ligands described above are capable of forming metal complexes. The present invention therefore also relates to metal complexes comprising a metal, a ligand of formula 1 and optionally at least one organic ligand L and / or at least one halogen X.

[0174] More particularly, the present invention also relates to transition metal complexes comprising a transition metal and a ligand of formula 1 and optionally at least one organic ligand L and / or at least one halogen X.

[0175] Even more particularly, the transition metal is a noble metal.

[0176] Yet even more specifically, in the transition metal complex of formula 1, the transition metal is selected from the group consisting of ruthenium, osmium, rhodium, nickel, iridium, palladium, platinum, silver and gold, specifically selected from the group consisting of rhodium, iridium, palladium and gold.

[0177] In the transition metal complex having the ligand of Formula 1, the organic ligand may be selected from the group consisting of dibenzylideneacetone (DBA), acetylacetone (acac), p-tolyl, m-tolyl, o-tolyl, cyclooctadiene (COD), and carbon monoxide.

[0178] In the transition metal complex having the ligand of formula 1, the halogen X is chlorine or bromine.

[0179] The present invention also relates to a method for carrying out a coupling reaction using a ligand as described above, preferably present in a metal complex, in particular a metal complex as described above.

[0180] More specifically, the present invention also relates to a method for performing a coupling reaction, comprising the following steps:

[0181] - providing a reaction mixture comprising at least a substrate, a coupling partner and a metal complex comprising a ligand as described herein, in particular a ligand according to any one of clauses 1 to 26 above; and

[0182] - reacting the substrate with the coupling partner in the presence of the metal complex or a derivative thereof to form a coupling product.

[0183] In the method of performing the coupling reaction, the metal complex comprising the ligand is a metal complex as described above, in particular a metal complex as defined in any one of items 27 to 31 above.

[0184] The substrate may be a substituted unsaturated or substituted aromatic compound, and in particular the substituted aromatic compound may be an aromatic or heteroaromatic compound.

[0185] Wherein, the substrate may be substituted by a leaving group or an unsaturated aliphatic group, whereby it is useful if the leaving group is selected from the group consisting of halogen (particularly Cl, Br or I (chlorine, bromine, iodine)), triflate, tosylate, norsulfonate and mesylate, and / or the unsaturated aliphatic group is selected from the group consisting of olefins or alkynes, particularly olefins or alkynes having 2 to 12, in particular 2 to 8, carbon atoms.

[0186] The coupling partner may comprise an organometallic compound, which may in particular be selected from the group consisting of organoboron compounds, organolithium compounds, organozinc compounds, organolithium compounds and Grignard's compounds, wherein advantageously the organometallic compound comprises at least one aromatic group, or wherein the organometallic compound comprises at least one unsaturated aliphatic group, or wherein the organometallic compound comprises at least one saturated aliphatic group.

[0187] Specifically, in the method for performing a coupling reaction, the coupling reaction may be selected from the group consisting of:

[0188] (i) Catalytic hydrofunctionalization of alkynes and alkenes;

[0189] (ii) Catalytic hydroamination of alkynes and alkenes;

[0190] (iii) catalytic OH addition reactions of alkynes and alkenes;

[0191] (iv) catalyzing coupling reactions;

[0192] (v) catalyzed Kumada coupling reaction, Murahashi coupling reaction, Negishi coupling reaction or Suzuki coupling reaction, especially for the production of biarylene;

[0193] (vi) catalyzing cross-coupling reactions, in particular CN and CO coupling reactions; and / or

[0194] (vii) Catalysis of Heck coupling reactions, particularly for the preparation of arylated alkenes, and Sonogashira coupling reactions, particularly for the preparation of arylated and olefinated alkynes.

[0195] (viii) Catalytic α-arylation of carbonyl compounds and imines.

[0196] More specifically, the ligands and transition metal complexes thereof, particularly palladium complexes thereof, are particularly useful for catalyzing the α-arylation of carbonyl compounds and imines, particularly carbonyl compounds, and more particularly ketones. They have been found to be particularly useful in the arylation of acetone. For this purpose, ligands of formula 2 have been found to be particularly useful:

[0197]

[0198] wherein A is methyl or o-tolyl, B is cyclohexyl or isopropyl, and C is piperidinyl or morpholinyl, both of which are attached to the P atom via their ring nitrogen atoms, such as compounds wherein A, B and C are as defined in the following table:

[0199] serial number A B C 1 methyl Cyclohexyl Piperidinyl 2 methyl Isopropyl Piperidinyl 3 methyl Cyclohexyl Morpholinyl 4 methyl Isopropyl Morpholinyl 5 o-Tolyl Cyclohexyl Piperidinyl 6 o-Tolyl Isopropyl Piperidinyl 7 o-Tolyl Cyclohexyl Morpholinyl 8 o-Tolyl Isopropyl Morpholinyl

[0200] These ligands are used in transition metal complexes as defined above.

[0201] The present invention is explained in more detail in the following examples. These are examples of ligands, their preparation and their metal complexes, their preparation and their use in catalysis. These examples should in no way be construed as limiting the scope of the present invention.

[0202] Examples

[0203] Synthesis and characterization of amine and phosphine precursors:

[0204] Synthesis of 10-P:

[0205]

[0206] N, N'-dimethylethane-1,2-diamine (2.47g, 3.02ml, 27.2mmol) and triethylamine (6.59g, 9.15ml, 64.8mmol) were dissolved in Et2O (150ml). CyPCl2 (4.80g, 4.00ml, 25.9mmol) was slowly added at -94°C to obtain a colorless suspension which was heated to room temperature overnight. The solid was filtered out and extracted with Et2O (3×20ml). The solvent was removed in vacuo and the oily residue was purified by Cugroll distillation (60°C, 1.0·10 -3 The product was obtained as a colorless oil.

[0207] Yield: (2.85 g, 14.2 mmol, 55%).

[0208] 1 H NMR (400MHz, C6D6): δ = 3.06–2.98 (m, 2H, NCH2), 2.70–2.56 (m, 8H, NCH2, NCH3), 1.89–1.73 (m, 4H, Cy,H2+3),1.66–1.58(m,1H,Cy,H4),1.44–1.35(m,1H,Cy,H1),1.29–1.14(m,5H,Cy,H2+3+4)ppm. 13 C{ 1 H}NMR (101MHz, C6D6): δ = 54.8 (d,2 J CP =7.0Hz,NCH2),41.7(d, 1 J CP =21.2Hz,Cy,C1),40.7(d, 2 J CP =26.6Hz,NCH3),27.6(d, 3 J CP =17.4Hz,Cy,C3),27.1–26.9(m,Cy,C2+4)ppm. 31 P{ 1 H} NMR (162MHz, C6D6): δ = 132.4ppm. IR(ATR):2918(s),2846(s),2788(m),1445(m),1149(s),1006(m),973(m),924(m),901(m),850(m),674(m),631(s),513(m),445(w)cm -1 .

[0209] Synthesis of 11-P:

[0210]

[0211] N, N'-diisopropylethylenediamine (7.98g, 10.0ml, 53,7mmol) and triethylamine (16.4g, 22.8ml, 161mmol) are dissolved in Et2O (250ml) and cooled to 0°C. Phosphorus trichloride (8.11g, 5.17ml, 59.1mmol) is added dropwise, and the colorless suspension is stirred at room temperature overnight. The solid is filtered out, extracted with Et2O (3×50ml), and all volatiles are removed in vacuo to obtain a yellow oil. The compound is redissolved in Et2O (150ml) and cooled to 0°C. CyMgCl (1.35M in Et2O, 39.8ml, 53.7mmol) is slowly added, and the suspension is warmed to room temperature overnight. The solid is filtered out, extracted with Et2O (3×50ml), and the solvent is removed in vacuo. The brown oily residue was extracted with pentane (3 x 30 ml). The solvent was evaporated in vacuo and the residue was purified by Kugelrohl distillation (100°C, 1.0 x 10 -3 The product was obtained as a colorless oil.

[0212] Yield: (7.77 g, 30.3 mmol, 57%).

[0213] 1H NMR(400MHz,C6D6):δ=3.20–3.00(m,4H,CH(CH3)2+NC2H4N),2.73–2.64(m,2H,NC2H4N),1.96–1.86(m,2H,Cy,H3 直立 ),1.86–1.79(m,2H,Cy,H2 直立 ),1.69–1.62(m,1H,Cy,H4 直立 ),1.43–1.32(m,1H,Cy,H1),1.29–1.17(m,5H,Cy,H 平伏 ),1.13(dd, 3 J HH =17.4Hz, 4 J HP =6.5Hz,12H,CH(CH3)2)ppm。 13 C{ 1 H}NMR(101MHz,C6D6):δ=52.4(d, 2 J CP =23.0Hz,CH(CH3)2),50.1(d, 2 J CP =6.5Hz,NC2H4N),41.4(d, 1 J CP =14.5Hz,Cy,C1),28.1(d, 3 J CP =17.8Hz,Cy,C3),27.2(d, 2 J CP =11.4Hz,Cy,C2),27.2(d, 4 J CP =1.4Hz,Cy,C4),23.7(d, 3 J CP =14.0Hz,CH(CH3)2),23.4(d, 3 J CP =6.5Hz,CH(CH3)2)ppm。 31 P{ 1 H}NMR(162MHz,C6D6):δ=107.7ppm。IR(ATR):2961(m),2918(s),2847(m),1447(m),1379(m),1359(m)1262(w),1166(s),1119(w),996(m),926(w),850(m),810(w),749(w),642(m),515(m)cm -1 。

[0214] Synthesis of N,N'-diisopentylethane-1,2-diamine

[0215]

[0216] Ethylenediamine (1.80 g, 2.00 ml, 60.1 mmol) and 3-methylbutanal (5.92 g, 7.44 ml, 68.8 mmol) were dissolved in methanol (200 ml). The solution was stirred at room temperature overnight. Sodium borohydride (5.95 g, 150 mmol) was added in batches, and the suspension was then refluxed for 2 hours. Water (100 ml) was added, and the mixture was extracted with hexane (3 × 200 ml). The organic phase was washed with saturated sodium chloride solution (100 ml), dried over magnesium sulfate, and the solvent was removed in vacuo. The crude product was obtained as a colorless oil and was used without further purification. 1 H and 13 C NMR spectroscopy indicated a purity of approximately 75%.

[0217] Yield (crude): (4.79 g, 18.0 mmol, 60%).

[0218] 1 H NMR (400MHz, CDCl3): δ=2.69(s,2H,NC2H4N)),2.60–2.55(m,2H,NCH2CH2),1.65–1.49(m,2H,CH(CH3)2),1.38–1.30(m,2H,NCH2CH2),0.86(d, 3 J HH =6.6Hz,12H,CH(CH3)2)ppm. 13 C{ 1 H} NMR (101MHz, CDCl3): δ = 49.9 (s, NC2H4N), 48.3 (s, NCH2CH2), 39.4 (s, NCH2CH2), 26.3 (s, CH (CH3)2), 22.8 (s, CH (CH3)2) ppm.

[0219] Synthesis of 12-Cl:

[0220]

[0221] N, N'-diisopentylethylenediamine (15.5g, 77,4mmol) and triethylamine (19.7g, 27.3ml, 193mmol) were dissolved in Et2O (250ml) and cooled to 0°C. Phosphorus trichloride (10.6g, 6.76ml, 77.4mmol) was added dropwise to give a colorless suspension which turned yellow within 1 hour. After the suspension was allowed to warm to room temperature within 2 hours, the suspension was filtered and the off-white solid was extracted with Et2O (3×50ml). All volatiles in the combined orange filtrate were removed in vacuo. The brown oily residue was purified by Kugerall distillation (100°C, 1.0·10 -3 The product was obtained as a colorless oil.

[0222] Yield: (5.74 g, 21.7 mmol, 28%).

[0223] 1 H NMR (400MHz, C6D6): δ=3.15–3.02(m,2H,NC2H4N),2.94–2.81(m,4H,NCH2CH2),2. 80–2.68(m,2H,NC2H4N),1.5–1.4(m,2H,CH),1.44–1.36(m,4H,NCH2CH2),0.79(d, 3 J HH =6.5Hz,12H,CH3)ppm. 13 C{ 1 H}NMR (101MHz, C6D6): δ = 50.1 (d, 2 J CP =10.5Hz,NCH2CH2),45.9(d, 2 J CP =16.0Hz,NC2H4N),37.9(d, 3 J CP =10.1Hz,NCH2CH2),26.1(s,CH),22.6(d, 5 J CP =27.4Hz,CH3)ppm. 31 P{ 1 H} NMR (162MHz, C6D6): δ = 163.0ppm. IR(ATR):2954(s),2867(m),1466(m),1366(m),1145(s),1121(s),1061(s),699(m),413(s)cm -1 .

[0224] Synthesis of 12-P:

[0225]

[0226] Chlorophosphine 12-Cl (4.58 g, 17.3 mmol) was dissolved in Et2O (100 ml) and cooled to 0 ° C. CyMgCl (1.35 M in Et2O, 12.8 ml, 17.3 mmol) was slowly added and the resulting suspension was allowed to warm to room temperature within 2 hours. The solid was filtered out, extracted with Et2O (3 × 20 ml), and the solvent was removed in vacuo. The brown oily residue was stirred in pentane (100 ml). The precipitated solid was filtered out and extracted with pentane (3 × 30 ml). The solvent of the gray filtrate was evaporated in vacuo, and the residue was purified by Kugerer distillation (120 ° C, 1.0 10 -3 The product was obtained as a colorless oil.

[0227] Yield: (3.80 g, 12.1 mmol, 70%).

[0228] 1 H NMR (400MHz, C6D6): δ=3.14–3.04(m,4H,NCH2CH2),2.88–2.78(m,2H,NC2H4N),2.72–2.66(m,2H,NC2H4N),1.98–1.91(m,2H,Cy,H3) ,1.84–1.78(m,2H,Cy,H2),1.72–1.61(m,3H,Cy,H4+CH),1.59–1.42(m,5H,Cy,H1+NCH2CH2),1.33–1.19(m,5H,Cy,H2+3+4),0.91(d, 3 J HH =6.6 Hz, 12H, CH3). 13 C{ 1 H}NMR (101MHz, C6D6): δ = 53.1 (d, 2 J CP =25.5Hz,NCH2CH2),52.7(d, 2 J CP =6.6Hz,NC2H4N),41.5(d, 1 J CP =16.8Hz,Cy,C1),40.6(d, 3 J CP =9.7Hz,NCH2CH2),),27.9(d, 4 J CP=17.6Hz,Cy,C3),27.1–27.0(m,Cy,C2+4),26.1(s,CH),22.9(d, 5 J CP =19.1Hz,CH3)ppm. 31 P{ 1 H}NMR (162MHz, C6D6): δ=128.7ppm. IR(ATR):2952(m),2919(s),2848(m),1447(w),1366(w),1151(s),1119(w)cm -1 .

[0229] Synthesis of 13-Cl:

[0230]

[0231] N, N'-di-neopentylethylenediamine (8.23g, 41.1mmol) and triethylamine (12.5g, 17.4ml, 123mmol) are dissolved in Et2O (300ml) and cooled to 0°C. Phosphorus trichloride (6.21g, 3.95ml, 45.2mmol) is added dropwise to give a colorless suspension which turns yellow within 1 hour. After the suspension is allowed to warm to room temperature within 2 hours, the suspension is filtered and the off-white solid is extracted with Et2O (3×50ml). The solvent of the combined orange filtrate is removed in vacuo. The brown oily residue is purified by Kugerrer sublimation (100°C, 1.0·10 -3 The product was purified by evaporation of the saturated benzene solution at 400 mbar. The product was obtained as a colorless crystalline solid. Colorless crystals suitable for single crystal X-ray diffraction experiments were obtained by slow evaporation of the saturated benzene solution.

[0232] Yield: (10.1 g, 38.1 mmol, 93%).

[0233] 1 H NMR (400MHz, C6D6): δ = 3.10–2.98 (m, 6H, NC2H4N+CH2), 2.37 (dd, 3 J HH =14.4,8.6Hz,2H,NC2H4N),0.81(s,18H,CH3)ppm. 13 C{ 1 H}NMR (101MHz, C6D6): δ = 59.9 (d, 2 J CP =14.3Hz,NC2H4N),54.2(d, 2 J CP =10.1Hz,CH2),33.0(d,3 J CP =6.6Hz,C(CH3)3),28.0(d, 4 J CP =1.8Hz,CH3)ppm. 31 P{ 1 H} NMR (162MHz, C6D6): δ = 172.9ppm. IR(ATR):2951(m),1477(m),1392(w),1362(m),1129(s),1077(m),1026(m),880(m),747(s),624(w),418(s),406(m)cm -1 Melting point: 83°C 12 H 26 Elemental analysis of ClN2P: Calculated values: C 54.43; H 9.90; N 10.58, Found values: C 54.02; H 10.27; N 10.62.

[0234] Synthesis of 13-P:

[0235]

[0236] Chlorophosphine 13-Cl (8.00 g, 30.2 mmol) and triethylamine (5.40 g, 7.50 ml, 53.1 mmol) were dissolved in Et2O (200 ml) and cooled to 0 ° C. CyMgCl (1.35 M in Et2O, 22.4 ml, 53.1 mmol) was slowly added and the resulting suspension was allowed to warm to room temperature within 2 hours. The solid was filtered out, extracted with Et2O (3 × 50 ml), and the solvent was removed in vacuo. The brown oily residue was stirred in pentane (100 ml). The precipitated solid was filtered out and extracted with pentane (3 × 30 ml). The solvent of the gray filtrate was evaporated in vacuo, and the residue was purified by Cugroll distillation (120 ° C, 1.0·10 -3 The product crystallized overnight and was obtained as a colorless solid.

[0237] Yield: (7.38 g, 23.6 mmol, 78%).

[0238] 1 H NMR (400MHz, C6D6): δ = 3.18–3.11 (m, 2H, NC2H4N), 3.06 (t, 3 J HP =13.7Hz, 4 J HH=0.9Hz,2H,NCH2),2.69–2.58(m,2H,NC2H4N),2.38(dd, 3 J HP =13.5Hz, 4 J HH =5.1Hz,2H,NCH2),2.05–1.95(m,2H,Cy,H3),1.83–1.76(m,2H,Cy,H2),1.66–1.59(m,1H ,Cy,H4),1.51–1.41(m,1H,Cy,H1),1.36–1.14(m,5H,Cy,H2+3+4),0.97(s,18H,CH3)ppm. 13 C{ 1 H}NMR (101MHz, C6D6): δ = 70.7 (d, 2 J CP =26.8Hz,NCH2),57.0(d, 2 J CP =6.7Hz,NC2H4N),41.9(d, 1 J CP =13.3Hz,Cy,C1),34.4(d, 3 J CP =7.6Hz,C(CH3)3),28.5(d, 3 J CP =17.0Hz,Cy,C3),28.3(s,CH3),27.2(d, 2 J CP =11.1Hz,Cy,C2),26.9(d, 4 J CP =1.0Hz,Cy,C4)ppm. 31 P{ 1 H} NMR (162MHz, C6D6): δ = 147.7ppm. IR(ATR):2914(s),2847(m),1474(w),1444(m),1389(m),1360(s),1207(m), 1141(s),981(s),873(s),852(m),714(s),581(m),520(m),411(w),403(m)cm -1 Melting point: 35°C 18 H 37 Elemental analysis of N2P: Calculated: C 69.19; H 11.93; N 8.96, Found: C 69.48; H 12.00; N 9.08.

[0239] Synthesis of 14-P:

[0240]

[0241] N,N'-dimesitylethane-1,2-diamine (7.71 g, 26.0 mmol) and triethylamine (6.61 g, 9.18 ml, 65.0 mmol) were dissolved in DCM (120 ml) and cooled to 0°C. CyPCl2 (4.82 g, 4.00 ml, 26.0 mmol) was added dropwise and the mixture was refluxed for 4 days. The solvent of the yellow mixture was removed in vacuo and the residue was extracted with THF (3×70 ml). The solvent of the filtrate was removed in vacuo and the residue was washed with Et2O (3×5 ml). The crude product was dissolved in hot Et2O (100 ml), filtered and slowly cooled to -30°C. Colorless crystals were formed, which were filtered off and washed with cold Et2O (3×10 ml). According to 31 P{ 1 H} NMR spectroscopy gave the product as colorless crystals with a purity of approximately 95% and was used without further purification. Colorless crystals suitable for single crystal X-ray diffraction experiments were obtained by recrystallization from hot Et2O.

[0242] Yield: (3.89 g, 9.52 mmol, 37%).

[0243] 1 H NMR (400MHz, C6D6): δ = 6.84 (s, 4H, CH, Mes 间位 ),3.54–3.48(m,2H,NCH2),2.90–2.84(m,2H,NCH2),2.72–2.27(m,12H,CH3,Mes 邻位 ),2.17(s,6H,CH3,Mes 对位 ),1.82–1.69(m,1H,Cy,H1),1.60–1.43(m,5H,Cy,H2+H4 平伏 ),1.25–1.11(m,2H,Cy,H3 平伏 ),1.03–0.87(m,3H,Cy,H3 直立 +H4 直立 )ppm. 13 C{ 1 H}NMR (101MHz, C6D6): δ = 141.8 (d, 2 J CP =14.4Hz,Mes 本位 ),136.1(s,Mes 邻位 ),134.2(d,J=1.7Hz,Mes对位 ),130.2(s,Mes 间位 ),52.9(d, 2 J CP =5.9Hz,NCH2),46.7(d, 1 J CP =37.4Hz,Cy,C1),27.4–26.4(m,Cy,C2-4),21.1–19.6(m,CH3,Mes 邻位,对位 )ppm. 31 P{ 1 H} NMR (162MHz, C6D6): δ = 106.1ppm.

[0244] Synthesis of 15-P:

[0245]

[0246] (1S,2S)-N,N'-dimethyl-1,2-cyclohexanediamine (2.86 g, 19.5 mmol) and triethylamine (4.96 g, 6.89 ml, 48.8 mmol) were dissolved in Et2O (100 ml) and cooled to 0°C. At this temperature, CyPCl2 was added dropwise to obtain a colorless suspension, which was allowed to warm to room temperature overnight. The solid was filtered and extracted with Et2O (3×50 ml). The solvent was removed in vacuo. The brown oily residue was purified by Cugroll distillation (105°C, 1.0·10 -3 The product was obtained as a colorless oil.

[0247] Yield: (3.71 g, 14.6 mmol, 75%)

[0248] 1 H NMR (400MHz, C6D6): δ=2.76–2.69(m,1H,Cy(NCH3)2,H1),2.64(d, 3 J HP =14.9Hz,3H,NCH3),2.51(d, 3 J HP =15.0Hz,3H,NCH3),2.13–2.05(m,1H,Cy(NCH3)2,H1),1.96–1.74(m,6H,Cy(NCH3 )2+Cy),1.68–1.50(m,4H,Cy(NCH3)2+Cy),1.40–0.90(m,9H,Cy(NCH3)2+Cy)ppm. 13 C{ 1 H}NMR (101MHz, C6D6): δ = 70.0 (d,2 J CP =3.6Hz,Cy(NCH3)2,C1),67.0(d, 2 J CP =7.3Hz,Cy(NCH3)2,C1),41.1(d, 1 J CP =27.6Hz,Cy,C1),39.2(d, 2 J CP =33.4Hz,NCH3),33.9(d, 2 J CP =19.0Hz,NCH3),31.2(s,Cy(NCH3)2,C2),29.1(d, 3 J CP =2.0Hz,Cy(NCH3)2,C2),28.6(d, 3 J CP =21.3Hz,Cy,C3),27.2–27.0(m,Cy,C2+4),26.9(d, 3 J CP =11.6Hz,Cy,C3),25.0(s,Cy(NCH3)2,C3),24.7(s,Cy(NCH3)2,C3)ppm. 31 P{ 1 H}NMR (162MHz, C6D6): δ=136.5ppm. IR(ATR):2919(s),2847(m),2787(w),1444(m),1204(w),1149(m),1023(w),996(m),972(s),879(w),725(s),680(m),514(w)cm -1 .

[0249] Synthesis of 16-P:

[0250]

[0251] Phosphorus trichloride (2.70g, 1.75ml, 20.0mmol) is dissolved in Et2O (150ml), and cooled to 0 DEG C.Morpholine (13.1g, 13.2ml, 150mmol) is slowly added, and white solid begins to precipitate.The suspension is stirred at room temperature for 1 hour, and solid is filtered out, and extracted with toluene (3 × 100ml).All volatiles are removed in vacuo, and the product as colorless solid is obtained.

[0252] Yield: (5.10 g, 17.6 mmol, 88%).

[0253] Synthesis of 17-P:

[0254]

[0255] At 0 ℃, N-methylaniline (17.2g, 17.5ml, 160mmol) and triethylamine (18.6g, 25.8ml, 183mmol) are dissolved in toluene (200ml). Phosphorus trichloride (6.28g, 4.00ml, 45.7mmol) is slowly added, and the resulting suspension is warmed to room temperature overnight. The solid is filtered out and extracted with hot toluene (3×200ml). The solvent is removed in a vacuum to obtain an orange viscous residue, which is washed with Et2O (3×50ml). The product is obtained as an off-white solid. By slowly evaporating the saturated benzene solution, colorless crystals suitable for single crystal X-ray diffraction experiments are grown.

[0256] Yield: (5.78 g, 16.53 mmol, 36%).

[0257] 1 H NMR (400MHz, CD2Cl2): δ=7.29–7.21(m,6H,Ph 间位 ),7.07–7.01(m,6H,Ph 邻位 ),6.92(t, 3 J HH =7.3Hz,3H,Ph 对位 ),3.02(d, 3 J HP =2.6Hz,9H,NCH3)ppm. 13 C{ 1 H}NMR (101MHz, CD2Cl2): δ = 148.6 (d, 2 J CP =24.2Hz,Ph 本位 ),129.5(d, 4 J CP =1.8Hz,Ph 间位 ),120.7(d, 5 J CP =1.3Hz,Ph 对位 ),117.1(d, 3 J CP =16.8Hz,Ph 邻位 ),33.4(d, 2 J CP =5.0Hz,NCH3)ppm. 31 P{ 1H}NMR (162MHz, CD2Cl2): δ=104.4ppm. IR(ATR):1591(m),1485(m),1264(s),1177(m),1086(m),1063(s),1025(m),988(w),832(s),748(s),693(m),677(s),605(m),425(s)cm -1 . Melting point: 207℃.

[0258] Synthesis and characterization of phosphonium salts:

[0259] Synthesis of 1·H2:

[0260]

[0261] 9 grams of tripiperidylphosphine (31.8mmol, 1 equivalent) are dissolved in 40ml THF and slowly added to a solution of 7.6ml (63.6mmol, 2 equivalents) benzyl bromide in 40ml THF at 0 ° C. It is stirred at room temperature for 1 hour, and a beige solid is precipitated. The suspension is filtered, and the residue is dissolved in 4ml DCM and filtered while hot. The solution is covered with 10ml pentane. After one day, a white solid precipitates. The solution is filtered out, and the solid is washed with 2 × 20ml pentane. 1 H2 (12.1g, 27.56mmol, 86%) is obtained as a colorless solid.

[0262] 1 H-NMR (400 MHz, chloroform-d): δ = 1.52–1.73 (m, 18H, Pip CH2 H 2+3 ),3.12(q, 3 J=5.9Hz,12H,Pip CH2 H3),4.39(d, 2 J HP =15.7Hz,2H,PCH2Ph),7.23–7.38(m,3H,Ph 对位+间位 CH),7.43–7.51(m,2H,Ph 邻位 CH). 13 C-NMR (101 MHz, chloroform-d): δ = 23.8 (d, 4 J CP =1.2Hz,Pip CH2C3),25.8(d, 3 J CP =5.1Hz,Pip CH2 C2),30.2(d, 1 J CP=100.7Hz,PCH2Ph),46.9(s,Pip CH2C1),128.1(d, 2 J=3.6Hz,Ph 对位 CH),129.0(s,Ph 本位 C),129.0(d, 4 J CP =3.2Hz,Ph 间位 CH),130.8(d, 3 J CP =6.1Hz,Ph 邻位 CH). 31 P-NMR (162 MHz, chloroform-d): δ = 50.4 (s). IR (ATR) [cm -1 ]:2937(m),1453(w),1334(w),1206(w),1157(m),1107(m),1072(s),951(s),1024(w),795(m),705(m),527(w),493(m),462(w). CHNS: Calculated: C: 58.15, H: 8.21, N: 9.25. Measured: C: 57.95, H: 8.15, N: 9.53. Melting point: 209.9°C.

[0263] 2·H2 Synthesis of:

[0264]

[0265] 4.5 g of tripiperidylphosphine (15.9 mmol, 1 equivalent) was dissolved in 80 ml of toluene. 1.53 ml of iodoethane (19.1 mmol, 1.2 equivalents) was slowly added, and the solution was stirred at room temperature overnight. The precipitated colorless solid was then filtered off, washed with 3 x 10 ml of pentane, and dried in vacuo. 2·H2 (6.11 g, 13.91 mmol, 88%) was obtained as a colorless solid.

[0266] 1 H NMR (400MHz, CDCl3): δ = 3.07 (q, J HH =6.1 Hz, 12H, Pip position 1 CH2), 2.61 (dq, J = 13.4, 7.6 Hz, 2H, P–CH2–CH3), 1.68–1.46 (m, 18H, Pip position 2 + position 3 CH2), 1.25–1.09 (m, 3H, CH3). 13 C NMR (101MHz, CDCl3): δ = 46.3 (d, 2 J CP=1.4Hz,Pip position 1CH2),25.9(d, 3 J CP =4.8Hz,Pip position 2CH2),23.7(d, 4 J CP =1.1Hz,Pip position 3CH2),18.0(d, 1 J CP =105.3Hz,P–CH2–CH3),6.6(d, 3 J CP =5.4Hz,CH3). 31 P NMR (162MHz, CDCl3): δ=54.5 (s).

[0267] Synthesis of 3·H2:

[0268]

[0269] 3.08ml cyclohexyldichlorophosphine (20mmol, 1 equivalent) and 7ml triethylamine (50mmol, 2.5 equivalents) are dissolved in 30ml ether and cooled to 0 ° C. A solution of 2.22ml N, N-dimethylethane -1,2- diamine (20mmol, 1 equivalent) in 50ml ether is prepared and slowly added over a period of 1 hour at 0 ° C by adding a funnel. During the addition, a colorless solid is precipitated. The mixture is stirred at room temperature overnight. The solid is filtered out, and 3.6ml benzyl bromide (30mmol, 1.5 equivalents) is added to the solution. It is stirred overnight, and a colorless solid is precipitated during this period. The precipitated colorless solid is then filtered out, washed with 3 × 10ml THF, and dried in a vacuum. 3 H2 (5.4g, 14.54mmol, 73%) is obtained as a colorless solid. 3 H2 can be used without further purification.

[0270] Synthesis of 4·H2:

[0271]

[0272] 4.5ml cyclohexyldichlorophosphine (29.2mmol, 1 equivalent) and 12.4ml triethylamine (87.6mmol, 3 equivalents) are dissolved in 50ml ether and cooled to 0 ° C. A solution of 3.24ml N, N-dimethylethane -1,2- diamine (29.2mmol, 1 equivalent) in 70ml ether is prepared and slowly added over a period of 1 hour by adding a funnel at 0 ° C. During the addition, a colorless solid is precipitated. The mixture is stirred at room temperature overnight. The solid is filtered out, and 2.34ml iodoethane (29.2mmol, 1 equivalent) is added to the solution. It is stirred overnight, and a colorless solid is precipitated during this period. The precipitated colorless solid is then filtered out, washed with 3 × 10ml THF, and dried in a vacuum. 4 H2 (6.2g, 17.29mmol, 60%) is obtained as a colorless solid.

[0273] 1 H NMR (400MHz, CD2Cl2): δ = 3.39 (d, 3 J HP =7.4 Hz, 4H, MeN(CH2)2NMe), 2.97–2.91 (m (overlapping), 1H, Cy position 1CH), 2.89 (d, 3 J HP =9.6Hz,6H,NCHH3),2.67(p, 2 J HP =7.7Hz,2H,P-CH2-CH3),1.93–1.70(m,5H,Cy position 2+3+4CH2),1.49–1.18(m,5H,Cy position 2+3+4,CH2),1.10–0.98(m,3H,P-CH2-CH3). 13 C NMR (101MHz, CD2Cl2): δ = 51.1 (d, 2 J CP =5.0Hz,MeN(CH2)2NMe),37.0(d, 1 J CP =63.3Hz,Cy position 1CH),33.0(d, 2 J CP =6.2Hz,NCH3),25.7(d, 2 J CP =14.5Hz,Cy position 2CH2),25.5(d, 4 J CP =1.8Hz,Cy position 4CH2),25.2(d, 3 J CP =3.6Hz,Cy position 3CH2),16.3(d, 1 JCP =59.1Hz,P-CH2-CH3),4.7(d, 2 J CP =7.0Hz,P-CH2-CH3). 31 P NMR (162MHz, CD2Cl2): δ=84.0 (s). IR(ATR)[cm -1 ]:3437(w),2925(m),2855(w),2822(w),1480(w),1446(w),1359(w),1251(w),1211(m),1154(s),1044(vs),949(vs),889(w),849(w),773(s),733(m),634(w),526(m),476(m),432(w). CHNS: Calculated: C: 40.46, H: 7.36, N: 7.86. Measured: C: 40.37, H: 7.56, N: 7.95. Melting point: 191.6°C (decomposition).

[0274] Synthesis of 5·H2:

[0275]

[0276] 5 g of tripiperidinylphosphine (17.6 mmol, 1 equivalent) was dissolved in 80 ml of toluene. 2.44 ml of 1-iodo-2-methylpropane (21.1 mmol, 1.2 equivalents) was slowly added, and the solution was stirred under reflux overnight. The precipitated beige solid was then filtered off, washed with 3 x 10 ml of pentane, and dried in vacuo. 5·H2 (7.35 g, 15.73 mmol, 89%) was obtained as a crystalline off-white solid.

[0277] 1 H NMR (400MHz, CD2Cl2): δ = 3.10 (q, J HH =5.7Hz,12H,Pip position 1CH2),2.37(dd, 2 J HP =13.8,J HH =6.2Hz,2H,P-CH2-iPr),2.02(tp, 3 J HP =13.1Hz,J HH =6.5Hz,1H,iPr CH,1.66(m,6H,Pip position 2CH2),1.60(q(br),J HH =5.4Hz,12H,Pip position 3CH2),1.14(d,J HH =6.7 Hz, 6H, iPr CH3).13 C NMR (101MHz, CD2Cl2): δ = 46.8 (d, 2 J CP =1.1Hz,Pip position 1CH2),31.7(d, 1 J CP =100.6Hz,P-CH2-iPr),26.0(d, 2 J CP =5.1Hz,Pip position 2CH2),24.6(d, 3 J CP =9.8Hz,iPr CH3),24.0(d, 4 J CP =1.2Hz,Pip position 3CH2),23.7(d, 2 J CP =3.4Hz,iPr CH). 31 P NMR (162MHz, CD2Cl2): δ=52.5 (s). IR(ATR)[cm -1 ]:3851(w),2929(w),2848(w1451(w),1377(w),1332(w),1284(w),1201(w),1155(w),1103(w),1073(s),1024(w),940(vs),836(w),815(w),779(w),711(w),663(w),564(w),530(w),486(w),462(w). CHNS: Calculated: C: 48.82, H: 8.41, N: 8.99. Measured: C: 48.82, H: 8.49, N: 8.74. Melting point: 195.5°C.

[0278] Synthesis of 7·H2:

[0279]

[0280] 3.5 g of tripiperidinylphosphine (12.4 mmol, 1 equivalent) was dissolved in 50 ml of THF. 2.42 ml of 2-methylbenzyl chloride (18.6 mmol, 1.5 equivalents) was slowly added, and the solution was stirred under reflux for 2 days. The precipitated beige solid was then filtered out, washed with 3 x 10 ml of pentane, and dried in vacuo. 7 H2 (3.72 g, 8.77 mmol, 71%) was obtained as an off-white solid.

[0281] 1 H NMR (400MHz, CD2Cl2): δ = 7.44–7.07 (m, 4H, CHoTol), 3.87 (d,2 J HP =15.7Hz,2H,PCH2),3.05(q, 3 J=5.8Hz,12H,CH2 Pip position 1),2.45(d, 4 J = 1.4 Hz, 3H, CH3oTol), 1.69–1.62 (m, 6H, CH2 Pip position 3), 1.61–1.53 (m, 12H, CH3Pip position 2). 13 C NMR (101MHz, CD2Cl2): δ = 137.4 (d, 2 J CP =7.7Hz,CoTol position 1),131.8(d, 3 J CP =2.6Hz,CH oTol position 6), 130.5(d,J=5.1Hz,CH oTol position 4), 128.9(d,J=3.5Hz,CH oTol position 3), 127.8(d, 3 J CP =7.7Hz,CoTol position 2), 127.1(d,J=3.3Hz,CH oTol position 5), 47.3(s,CH2 Pip position 1), 27.6(d, 1 J CP =108.1Hz,PCH2),26.1(d, 3 J CP =5.1Hz,CH2,Pip position 2),24.1(d, 3 J CP =1.2Hz,CH2 Pip position 3), 21.1(s,CH3oTol). 31 P NMR (162MHz, CD2Cl2): δ=50.0 (s, Pip3P). IR(ATR)[cm -1 ]:2928(w),2857(w),1494(w),1451(w),1362(w),1336(w),1196(w),1162(w),1099(w),10 71(s),952(vs),860(w),810(w),783(w),744(w),712(w),559(w),539(w),471(w),442(m). Melting point: 153.8℃.

[0282] Synthesis of 10·H2:

[0283]

[0284] A solution of 2-methylbenzyl iodide (2.48 g, 10.7 mmol) in THF (30 ml) was added to a solution of 10-P (2.15 g, 10.7 mmol) in THF (30 ml). The resulting colorless suspension was stirred at room temperature overnight. The colorless solid was filtered out and washed with THF (3 × 20 ml). The phosphonium salt 10 H2 was obtained as a colorless solid. Colorless crystals suitable for single crystal X-ray diffraction experiments were obtained by slow vapor diffusion of Et2O into a saturated acetonitrile solution of the compound.

[0285] Yield: (4.58 g, 10.6 mmol, 99%).

[0286] 1 H NMR (400MHz, CDCl3): δ = 7.23–7.18 (m, 1H, oTol 邻位 ),7.15–7.05(m,3H,oTol 间位 + 对位 ),4.15(d, 2 J HP =10.9Hz,2H,CH2oTol),3.58–3.45(m,1H,Cy,H1),3.2–3.1(m,2H,NC2H4N),2.9(d, 3 J HP =9.5Hz,6H,NCH3),2.9–2.8(m,2H,NC2H4N),2.33(s,3H,CH3),2.05–1.95(m,2H,Cy),1.86 –1.67(m,3H,Cy),1.60–1.47(m,2H,Cy),1.41–1.27(m,2H,Cy),1.25–1.12(m,1H,Cy)ppm. 13 C{ 1 H}NMR (101MHz, CDCl3): δ = 137.2 (d, 2 J CP =5.8Hz,oTol 本位 ),131.1(d, 4 J CP =3.1Hz,oTol 间位 ),130.6(d, 3 J CP =5.1Hz,oTol 邻位 ),128.1(d, 4 J CP =3.5Hz,oTol 间位' ),126.4(d, 3 J CP =10.6Hz,oTol邻位' ),126.3(d, 5 J CP =3.3Hz,oTol 对位 ),50.6(d, 2 J CP =4.6Hz,NC2H4N),36.8(d, 1 J CP =59.1Hz,Cy,C1),33.5(d, 2 J CP =6.4Hz,NCH3),29.0(d, 1 J CP =54.6Hz,CH2oTol),25.7–25.2(m,Cy,C2-4),20.7(d, 4 J CP =1.4Hz,CH3)ppm. 31 P{ 1 H} NMR (162MHz, CDCl3): δ = 78.2ppm. IR(ATR):2851(w),1446(m),1250(m),1223(m),1203(m),1160(m),1144(m),1037(s),948(s),86 1(m),803(s)772(m)759(m),706(w),640(w),603(w),553(m),505(w),466(s),419(m),409(w)cm -1 Melting point: 226°C 18 H 30 Elemental analysis of IN2P: Calculated: C 50.01; H 6.99; N 6.48, Found: C 50.08; H 6.86; N 6.45.

[0287] Synthesis of 11·H2:

[0288]

[0289] A solution of 2-methylbenzyl iodide (6.34 g, 27.3 mmol) in toluene (50 ml) was transferred to a solution of 11-P (7.00 g, 27.3 mmol) in toluene (100 ml). After a few minutes, a colorless solid began to precipitate, and the mixture was stirred at room temperature for 72 hours. The colorless solid was filtered out and washed with toluene (3 × 20 ml) and pentane (3 × 20 ml). The phosphonium salt 11 H2 was obtained as a colorless solid. By slowly diffusing pentane vapor into a saturated THF solution of the compound, colorless crystals suitable for single crystal X-ray diffraction experiments were obtained.

[0290] Yield: (12.7 g, 25.9 mmol, 95%).

[0291] 1 1H NMR (400 MHz, CDCl3): δ = 7.18–7.08 (m, 4H, oTol), 4.06 (d, 1 J HP = 10.8 Hz, 2H, CH2oTol), 3.86–3.76 (m, 2H, CH(CH3)2), 3.55–3.43 (m, 1H, Cy, H1), 3.32–3.20 (m, 4H, NC2H4N), 2.41 (s, 3H, CH3), 2.18–2.​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​CP =61.6Hz,Cy,C1),27.2(d, 1 J CP =56.9Hz,CH2oTol),25.8(d, 3 J CP =3.6Hz,Cy,C3),25.7–25.6(m,Cy,C2),25.5(s,Cy,C4)21.6(d, 3 J CP =2.7Hz,CH(CH3)2),21.2(s,CH3),20.6(d, 3 J CP =3.3Hz,CH(CH3)2)ppm. 31 P{ 1 H} NMR (162MHz, CDCl3): δ = 74.5ppm. IR(ATR):2932(w),1398(m),1366(w),1197(m),1162(s),1115(s),1057(m), 880(w),790(w),766(w),747(m),737(m),546(m),522(w),509(m),470(s)cm -1 Melting point: 160°C 22 H 38 Elemental analysis of IN2P: Calculated: C 54.10; H 7.84; N 5.74, Found: C 54.35; H 7.78; N 5.67.

[0292] Synthesis of 12·H2:

[0293]

[0294] A solution of 2-methylbenzyl iodide (3.27 g, 14.1 mmol) in Et2O (30 ml) was transferred to a solution of phosphine 12-P in Et2O (100 ml). After a few minutes, a colorless solid began to precipitate, and the suspension was stirred at room temperature overnight. The colorless solid was filtered out and washed with Et2O (3 × 50 ml). The crude product was extracted with hot THF (30 ml), and the filtrate was slowly cooled to -30 ° C. Colorless crystals were formed, filtered out and washed with cold THF (3 × 5 ml). After drying in a vacuum at 140 ° C for 10 hours, phosphonium salt 12 H2 was obtained as a colorless solid. By recrystallization from hot toluene, colorless crystals suitable for single crystal X-ray diffraction experiments were obtained.

[0295] Yield: (3.86 g, 7.08 mmol, 50%).

[0296] <h2 style=";text-align:left;direction:ltr"> 1 <h2 style=";text-align:left;direction:ltr"> H NMR(400MHz,CDCl3):δ=7.24–7.14(m,4H,oTol),4.19(d,<h2 style=";text-align:left;direction:ltr"> 2 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> HP <h2 style=";text-align:left;direction:ltr"> =10.9 Hz, 2H, CH2oTol), 3.67–3.57 (m, 1H, Cy, H1), 3.36–3.22 (m, 4H, N-C-H-O-N ...<h2 style=";text-align:left;direction:ltr"> 3 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> HH <h2 style=";text-align:left;direction:ltr"> =6.6,3.0Hz,12H,CH(CH3)2)ppm。<h2 style=";text-align:left;direction:ltr"> 13 <h2 style=";text-align:left;direction:ltr"> C{<h2 style=";text-align:left;direction:ltr"> 1 <h2 style=";text-align:left;direction:ltr"> H}NMR(101MHz,CDCl3):δ=137.2(d,<h2 style=";text-align:left;direction:ltr"> 2 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> CP <h2 style=";text-align:left;direction:ltr"> <6.3Hz, oTol<h2 style=";text-align:left;direction:ltr"> 本位 <h2 style=";text-align:left;direction:ltr"> ),131.4(d,<h2 style=";text-align:left;direction:ltr"> 4 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> CP <h2 style=";text-align:left;direction:ltr"> <2.8Hz, oTol<h2 style=";text-align:left;direction:ltr"> 间位 <h2 style=";text-align:left;direction:ltr"> ),129.9(d,<h2 style=";text-align:left;direction:ltr"> 3 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> CP <h2 style=";text-align:left;direction:ltr"> <5.1Hz, oTol<h2 style=";text-align:left;direction:ltr"> 邻位 <h2 style=";text-align:left;direction:ltr"> ),128.2(d,<h2 style=";text-align:left;direction:ltr"> 4 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> CP <h2 style=";text-align:left;direction:ltr"> <3.3Hz, oTol<h2 style=";text-align:left;direction:ltr"> 间位' <h2 style=";text-align:left;direction:ltr"> ),127.0(d,<h2 style=";text-align:left;direction:ltr"> 3 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> CP <h2 style=";text-align:left;direction:ltr"> <9.9Hz, oTol<h2 style=";text-align:left;direction:ltr"> 邻位' <h2 style=";text-align:left;direction:ltr"> ),126.5(d,<h2 style=";text-align:left;direction:ltr"> 5 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> CP <h2 style=";text-align:left;direction:ltr"> <3.0Hz, oTol<h2 style=";text-align:left;direction:ltr"> 对位 <h2 style=";text-align:left;direction:ltr"> ),47.4(d,<h2 style=";text-align:left;direction:ltr"> 2 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> CP <h2 style=";text-align:left;direction:ltr"> <5.1Hz,NC2H4N),44.6(d,<h2 style=";text-align:left;direction:ltr"> 2 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> CP <h2 style=";text-align:left;direction:ltr"> <5.1Hz,NCH2CH2),37.6(d,<h2 style=";text-align:left;direction:ltr"> 1 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> CP <h2 style=";text-align:left;direction:ltr"> =60.5Hz,Cy,C1),37.4(d,<h2 style=";text-align:left;direction:ltr"> 3 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> CP <h2 style=";text-align:left;direction:ltr"> <4.4Hz,NCH2CH2),28.6(d,1 J CP =54.0Hz,CH2oTol),26.1(s,CH(CH3)2),25.7–25.4(m,Cy,C2+3+4),22.7(d, 5 J CP =3.6Hz,CH(CH3)2),21.2(s,CH3)ppm. 31 P{ 1 H} NMR (162MHz, CDCl3): δ = 78.1ppm. IR(ATR):2925(m),2866(m),1460(m),1366(w),1161(m),1139(s),1069 (s),864(m),800(m),757(m),554(m),540(m),508(m),465(s),416(m)cm -1 Melting point: 154°C 26 H 46 Elemental analysis of IN2P: Calculated: C 57.35; H 8.51; N 5.14, Found: C 57.40; H 8.56; N 5.11.

[0297] Synthesis of 13·H2:

[0298]

[0299] Phosphine 13-P (6.47 g, 20.7 mmol) and iodoethane (9.69 mg, 4.97 ml, 62.1 mmol) were dissolved in toluene (70 ml). The solution was heated to 70 ° C for 5 days. The colorless suspension was filtered and the solid was washed with toluene (3 × 10 ml) and Et2O (3 × 10 ml). The phosphonium salt 13·H2 was obtained as a colorless solid. Colorless crystals suitable for single crystal X-ray diffraction experiments were obtained from the combined washing solutions.

[0300] Yield: (9.24 g, 20.7 mmol, 95%).

[0301] 1H NMR (400MHz, CDCl3): δ=3.55–3.41(m,4H,NC2H4N),3.12–2.74(m,7H,NCH2+Cy,H1+CH2CH3),2.08–1.97(m,2H,Cy,H2),1.83–1.65( m,3H,Cy,H3+4),1.54–1.39(m,2H,Cy,H3),1.38–1.27(m,2H,Cy,H2),1.20–1.02(m,4H,CH2CH3+Cy,H4),0.99(s,18H,C(CH3)3)ppm. 13 C{ 1 H}NMR (101MHz, CDCl3): δ = 58.8 (d, 2 J CP =3.0Hz,NCH2),52.1(d, 2 J CP =4.7Hz,NC2H4N),37.2(d, 1 J CP =62.3Hz,Cy,C1),33.8(d, 3 J CP =5.3Hz,C(CH3)3),28.5(s,C(CH3)3),25.5(d, 3 J CP =14.3Hz,Cy,C3),25.3(d, 4 J CP =1.8Hz,Cy,C4),24.9(d, 2 J CP =3.6Hz,Cy,C2),17.9(d, 1 J CP =58.2Hz,CH2CH3),4.7(d, 2 J CP =7.4Hz,CH2CH3)ppm. 31 P{ 1 H} NMR (162MHz, CDCl3): δ = 91.3ppm. IR(ATR):2940(w),1363(w),1128(s),1095(m),1032(m),887(m),849(w),791(m),736(m),564(m),471(m)cm -1 Melting point: 217°C 20 H 42 Elemental analysis of IN2P: Calculated: C 51.28; H 9.04; N 5.98, Found: C 51.31; H 9.31; N 5.98.

[0302] Synthesis of 14·H2:

[0303]

[0304] Phosphine 14-P (528 mg, 1.29 mmol) and iodoethane (2.01 g, 1.03 ml, 12.9 mmol) were dissolved in toluene (20 ml) and the mixture was heated to 60° C. overnight. All volatiles were removed in vacuo. The oily residue was suspended in Et2O (20 ml), frozen, and a colorless suspension was obtained when the mixture warmed to room temperature. The colorless solid was filtered off and washed with Et2O (3×10 ml). 31 P{ 1 H} NMR spectroscopy gave the crude phosphonium salt 14·H 2 as a colorless solid with a purity of 90%.

[0305] Yield: (300 mg, 0.478 mmol, 37%).

[0306] 1 H NMR (400MHz, CDCl3): δ = 6.94 (s, 4H, Mes 间位 ),4.05–3.86(m,4H,NCH2),2.65–2.52(m,2H,CH2CH3),2.47(s,6H,Mes 对位 ,CH3),2.44(s,6H,Mes 邻位 ,CH3),2.37–2.29(m,1H,Cy,H1),2.27(s,6H,Mes 邻位 ',CH3),1.77–1.66(m,3H,Cy,H3+4),1.59–1.50(m,2H,Cy,H2),1.33–1.13(m,8H,Cy,H2+3+4,CH2CH3)ppm. 13 C{ 1 H}NMR (101MHz, CDCl3): δ = 139.3 (d, 5 J CP =1.4Hz,Mes 对位 ),137.5(d, 3 J CP =1.8Hz,Mes 邻位 ),137.4(d, 3 J CP =2f.1Hz,Mes 邻位' ),132.7(d, 2 J CP =4.9Hz,Mes 本位),131.0(s,Mes 间位 ),130.6(s,Mes 间位 '),52.1(d, 2 J CP =8.4Hz,NCH2),41.9(d, 1 J CP =60.0Hz,Cy,C1),26.5(d, 3 J CP =14.0Hz,Cy,C3),26.2(d, 2 J CP =2.9Hz,Cy,C2),25.5(d, 4 J CP =1.8Hz,Cy,C4),21.7(d, 1 J CP =61.2Hz,CH2CH3),21.0(s,Mes 对位 ,CH3),20.1(s,Mes 邻位 ,CH3),19.4(s,Mes 邻位' ,CH3),7.6(d, 2 J CP =4.7Hz,CH2CH3)ppm. 31 P{ 1 H} NMR (162MHz, CDCl3): δ = 66.8ppm.

[0307] Synthesis of 15·H2:

[0308]

[0309] A solution of 2-methylbenzyl iodide (3.04 g, 13.1 mmol) in THF (30 ml) was added to a solution of phosphine 15-P (3.34 g, 13.1 mmol) in THF (30 ml). The resulting white suspension was stirred at room temperature overnight. The colorless solid was filtered out and washed with THF (3 × 20 ml). The phosphonium salt 15 H2 was obtained as a colorless solid. By slowly vapor diffusing Et2O into a saturated chloroform solution of the compound, colorless crystals suitable for single crystal X-ray diffraction experiments were obtained.

[0310] Yield: (6.33 g, 13.0 mmol, 99%). 1 H NMR (400MHz, CDCl3): δ=7.36–7.31(m,1H,oTol 邻位 ),7.21–7.10(m,3H,oTol 间位 + 对位<h2 style=";text-align:left;direction:ltr">),4.39–4.21(m,2H,Cy(NCH3)2,H1),3.68–3.58(m,1H,Cy,H1),2.92(d,<h2 style=";text-align:left;direction:ltr"> 3 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> HP <h2 style=";text-align:left;direction:ltr"> =10.9Hz,3H,NCH3),2.85(d,<h2 style=";text-align:left;direction:ltr"> 3 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> HP <h2 style=";text-align:left;direction:ltr"> =11.2 Hz, 3H, NCH3), 2.66–2.57 (m, 1H, Cy(NCH3)2, H1), 2.39 (s, 3H, CH3), 2.29–2.19 (m, 1H, Cy, H3), 2.12–2.02 (m, 1H, Cy(NCH3)2, H2), 2.01–1.75 (m, 9H, Cy(NCH3)2, H3+4, Cy, H2+ 3+4), 1.67–1.54(m,2H,Cy,H2+3+4), 1.51–1.34(m,2H,Cy,H2+3+4), 1.31–1.15(m,2H,Cy(NCH3)2,H4), 1.12–1.00(m,2H,Cy(NCH3)2,H3+4), 0.96–0.82(m,1H,Cy(NCH3)2,H3)ppm.<h2 style=";text-align:left;direction:ltr"> 13 <h2 style=";text-align:left;direction:ltr"> C{<h2 style=";text-align:left;direction:ltr"> 1 <h2 style=";text-align:left;direction:ltr"> H}NMR(101MHz,CDCl3):δ=137.6(d,<h2 style=";text-align:left;direction:ltr"> 2 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> CP <h2 style=";text-align:left;direction:ltr"> <5.5Hz, oTol<h2 style=";text-align:left;direction:ltr"> 本位 <h2 style=";text-align:left;direction:ltr"> ),131.3(d,<h2 style=";text-align:left;direction:ltr"> 3 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> CP <h2 style=";text-align:left;direction:ltr"> <4.9Hz, oTol<h2 style=";text-align:left;direction:ltr"> 邻位 <h2 style=";text-align:left;direction:ltr"> ),131.0(d,<h2 style=";text-align:left;direction:ltr"> 4 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> CP <h2 style=";text-align:left;direction:ltr"> <3.2Hz, oTol<h2 style=";text-align:left;direction:ltr"> 间位 <h2 style=";text-align:left;direction:ltr"> ),128.2(d,<h2 style=";text-align:left;direction:ltr"> 4 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> CP <h2 style=";text-align:left;direction:ltr"> <3.6Hz, oTol<h2 style=";text-align:left;direction:ltr"> 间位 <h2 style=";text-align:left;direction:ltr"> ),126.4(d,<h2 style=";text-align:left;direction:ltr"> 3 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> CP <h2 style=";text-align:left;direction:ltr"> <10.5Hz, oTol<h2 style=";text-align:left;direction:ltr"> 邻位' <h2 style=";text-align:left;direction:ltr"> ),126.1(d,<h2 style=";text-align:left;direction:ltr"> 5 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> CP <h2 style=";text-align:left;direction:ltr"> <3.3Hz, oTol<h2 style=";text-align:left;direction:ltr"> 对位 <h2 style=";text-align:left;direction:ltr"> ),66.5(d,<h2 style=";text-align:left;direction:ltr"> 2 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> CP <h2 style=";text-align:left;direction:ltr"> <3.0Hz,Cy(NCH3)2,C1),65.7(d,<h2 style=";text-align:left;direction:ltr"> 2 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> CP <h2 style=";text-align:left;direction:ltr"> <2.7Hz,Cy(NCH3)2,C1),36.5(d,<h2 style=";text-align:left;direction:ltr"> 1 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> CP=57.2Hz,Cy,C1),30.4(d, 2 J CP =4.3Hz,NCH3),30.2(d, 2 J CP =5.0Hz,NCH3),28.8(d, 1 J CP =52.9Hz,CH2oTol),27.77(d, 3 J CP =1.8Hz,Cy(NCH3)2,C2),27.71(d, 3 J CP =1.4Hz,Cy(NCH3)2,C2'),25.9(d, 3 J CP =4.0Hz,Cy,C3),25.7(d, 3 J CP =14.2Hz,Cy,C3),25.5–25.3(m,Cy,C2+4),23.6(d, 4 J CP =1.8Hz,Cy(NCH3)2,C3),20.8(d, 4 J CP =1.4Hz,CH3)ppm. 31 P{ 1 H} NMR (162MHz, CDCl3): δ = 78.7ppm. IR(ATR):2921(w),2854(w),1444(m),1246(w),1198(m),1170(m),1152(w),1120(w),1016(s) ,921(w),901(m),857(w),834(w),811(w),788(w),751(m),729(w),555(m),478(m),463(m)cm -1 Melting point: 273°C 22 H 36 Elemental analysis of IN2P: Calculated values: C 54.32; H 7.46; N 5.76, Found values: C 54.22; H 7.32; N 5.61.

[0311] Synthesis of 16·H2:

[0312]

[0313] Trimorpholinophosphine 16-P (3.00 g, 10.4 mmol) and 2-methylbenzyl iodide (2.41 g, 10.4 mmol) were dissolved in THF (70 ml) and stirred overnight. A colorless suspension was formed and filtered. The off-white solid was washed with THF (3 × 20 ml) and DCM (3 × 10 ml). After drying in vacuo at 100 ° C for 10 hours, the phosphonium salt 16 H2 was obtained as a colorless solid. By slowly vapor diffusing Et2O into a saturated acetonitrile solution of the compound, colorless crystals suitable for single crystal X-ray diffraction experiments were obtained.

[0314] Yield: (4.54 g, 8.70 mmol, 84%).

[0315] 1 H NMR (400MHz, CD3CN): δ = 6.97–6.84 (m, 4H, oTol), 3.51 (d, 1 J HP =15.5Hz,2H,CH2oTol),3.24–3.20(m,12H,Mor,H2),2.81–2.72(m,12H,Mor,H3),2.06(d, 3 J HH =1.4Hz,3H,CH3)ppm. 13 C{ 1 H}NMR (101MHz, CD3CN): δ = 138.6 (d, 2 J CP =8.6Hz,oTol 本位 ),132.4(d, 4 J CP =2.2Hz,oTol 间位 ),131.0(d, 3 J CP =5.1Hz,oTol 邻位 ),129.5(d, 4 J CP =3.2Hz,oTol 间位' ),128.1(d, 3 J CP =7.4Hz,oTol 邻位' ),127.8(d, 5 J CP =3.0Hz,oTol 对位 ),66.9(d, 2 J CP =5.3Hz,Mor,C2),46.5(Mor,C3),26.3(d, 1 J CP=105.7Hz, CH2oTol), 20.9(CH3)ppm. 31 P{ 1 H} NMR (162MHz, CD3CN): δ = 49.3ppm. IR(ATR):1353(w),1252(w),1131(m),1107(s),957(s),923(m),845(w),794(m),748(w),716(w),509(w),460(m)cm -1 Melting point: 252°C 20 H 33 Elemental analysis of IN3O3P: Calculated values: C 46.07; H 6.38; N 8.06, Found values: C 45.92; H 8.08; N 6.37.

[0316] Synthesis of 17·H2:

[0317]

[0318] Tri(N-methylaniline)phosphine 17-P (4.00 g, 11.4 mmol) and iodoethane (5.33 g, 2.74 ml, 34.2 mmol) were suspended in toluene (25 ml) and the mixture was heated to 90 ° C for 9 days. A brown solid was formed, which was separated from the brown solution. Acetonitrile (30 ml) was added and the resulting brown solution was treated with Et2O (100 ml). After filtration, crude 17·H2 was obtained as a brown solid and was used without further purification.

[0319] 18·H 2 Synthesis of:

[0320]

[0321] Iminobibenzyl (1.95g, 10mmol) is dissolved in THF (25ml), and slowly processed with n-BuLi (1.6M, 4.25ml, 10mmol) at-90 ℃. The gained colorless suspension is stirred 1 hour at-90 ℃, then iPrPCl (1.53ml, 10mmol) is added, and the reaction mixture is warmed to room temperature. Benzyl bromide is added, and the gained colorless suspension is stirred overnight. Colorless solid is filtered out, and washed with THF (3 × 10ml). Product is used for next step without further purification.

[0322] Synthesis and characterization of ligands :

[0323] Synthesis of L1:

[0324]

[0325] 5g (11mmol, 1 equivalent) phosphonium salt 1 H2 is suspended in 50ml THF and deprotonated by slowly adding 6.9ml n-BuLi solution (1.6M in hexane, 11mmol, 1 equivalent) until a clear light yellow solution is formed. The solution is stirred for 45 minutes, and then 2.42ml (11mmol, 1 equivalent) of the corresponding chlorophosphine is added at room temperature. Soon after the addition, a colorless solid precipitates. The suspension is stirred for 2 hours, and then 6.9ml n-BuLi solution (1.6M in hexane, 11mmol, 1 equivalent) is slowly added until a clear yellow solution is formed. The solution is stirred for 30 minutes, and the solvent is subsequently removed in a vacuum. The residue is suspended in 50ml acetonitrile and stirred overnight to form a colorless solid. The solid is filtered out, washed with 2×20ml acetonitrile, and dried in a vacuum to obtain L1 (4.87g, 8.55mmol, 78%) as a colorless solid.

[0326] 1 H-NMR (400MHz, CD2Cl2): δ = 0.96–1.36 (m, 10H, PCy2 CH2 H 2+3+4 ),1.49(q,12H, 3 J=5.4Hz,Pip CH2 H2),1.53–1.59(m,6H,Pip CH2 H3),1.59–1.68(m,6H,PCy2 CH2 H 2+3+4 ),1.69–1.77(m,2H,PCy2 CH2 H 2+3+4 ),1.80–1.89(m,3H,PCy2 CH2 H 2+3+4 ),2.18(tdt, 2 J HP =10.6Hz, 4 J HP =6.4Hz, 3 J=3.2Hz,2H,PCy2 CHH1),3.07(q, 3 J HP =5.4Hz,6H,Pip CH2 H1),6.47(m,1H,Ph 对位 ),6.88(m,2H,Ph 邻位 ),6.98(m,2H,Ph 间位 ). 13 C-NMR (101 MHz, methylene chloride-d2): δ = 25.4 (s, PipCH2 C3), 26.9 (d, 3 J CP=4.7Hz,Pip CH2 C2),27.2(d, 2 J=1.4Hz,PCy2CH2 C 2+3+4 ),27.8–28.4(m,PCy2CH2 C 2+3+4 ),31.7(m,PCy2CH2 C 2+3+4 ),34.9(m,PCy2CH2 C 2+3+4 ),36.0(dd, 1 J CP =14.4Hz, 3 J CP =8.5Hz,PCy2CHC1),38.4(dd, 1 J CP =173.8Hz,29.0Hz),48.4(dd, 2 J CP =5.8Hz, 3 J CP =1.4Hz,Pip CH2 C1),115.7(s,Ph 对位 ),124.0(d, 2 J CP =12.5Hz,Ph 邻位 ),127.4(d, 4 J CP =1.5Hz,Ph 间位 ),148.1(d, 2 J CP =13.2Hz,Ph 本位 ). 31 P-NMR (162 MHz, methylene chloride-d2): δ = -7.63 (d, 2 J PP =195.2Hz,PCy2),56.2(d, 2 J PP =195.5Hz,P(Pip)3). IR(ATR)[cm -1 ]:2915(m),2841(w),1589(w),1485(w),1232(m),1155(m),1116(w),1059(s),10 24(m),983(m),917(m),851(w),745(s),701(m),642(w),540(m),472(m),416(w). Melting point: 216.6℃. HRMS(ESI):m / z C 34 H 58 N3P2[M+H] + Calculated value: 570.4101; experimental value: 570.4092.

[0327] Synthesis of L2:

[0328]

[0329] 2.7g (6.15mmol, 1 equivalent) phosphonium salt 2 H2 is suspended in 40ml THF, and deprotonated by slowly adding 4ml n-BuLi solution (1.55M in hexane, 6.15mmol, 1 equivalent), until a clear solution is formed. The solution is stirred 45 minutes, and then 1.36ml dicyclohexyl chlorophosphine (6.15mmol, 1 equivalent) is added at room temperature. Soon after the addition, a colorless solid precipitates. The suspension is stirred 2 hours, and then 4ml n-BuLi solution (1.55M in hexane, 6.15mmol, 1 equivalent) is slowly added, until a clear yellow solution is formed. The solution is stirred 30 minutes, and subsequently the solvent is removed in a vacuum. Residue is suspended in 30ml acetonitrile and stirred overnight to form a colorless solid. The solid was filtered off, washed with 2 x 10 ml acetonitrile and dried in vacuo to give L2 (2.71 g, 5.34 mmol, 89%) as a colorless solid.

[0330] 1 H NMR (400MHz, THF): δ = 3.08 (q, 3 J=5.2Hz,12H,Pip position 1,CH2),1.86(d, 3 J = 11.7 Hz, 2H, Cy position 3, CH2), 1.78–1.63 (m, 10H, Cy position 1, CH+Cy position 2+position 3, CH2), 1.61–1.42 (m, 21H, CH3+Pip position 2+position 3, CH2), 1.33–1.11 (m, 10H, Cy position 3+position 2, CH2). 13 C NMR (101MHz, THF): δ = 48.6 (d, 2 J CP =5.1Hz,Pip position 1,CH2),35.6(dd, 1 J CP =13.8Hz, 3 J CP =8.8Hz,Cy position 1,CH),33.3(d, 2 J CP =19.9Hz,Cy position 2,CH2),32.2(d, 3 J CP =9.2Hz,Cy position 3,CH2),29.1(d, 3 J CP=6.9Hz,Cy position 3,CH2),28.9(d, 2 J CP =12.4Hz,Cy position 2,CH2),28.3(s,Cy position 4,CH2),27.9(d, 3 J CP =5.2Hz,Pip position 2,CH2),26.3(s,Pip position 3,CH2),15.4(d, 2 J CP =9.7Hz,CH3),13.5(dd, 1 J CP =195.5,19.8Hz,P–C - –P). 31 P NMR (162MHz, THF): δ = 60.9 (d, 2 J PP =191.8Hz,P + Pip3),-4.3(d, 2 J PP =192.0Hz,PCy2). IR(ATR)[cm -1 ]:3388(w),2917(m),2845(w),2821(w),1632(w),1442(w),1364(w),1325(w),1213(w),1153(w),1120(w),10 48(m),1024(w),935(vs),894(m),846(w),719(w),692(m),670(w),612(w),556(w),509(w),470(w),427(w). Melting point: 110.6℃. HRMS(ESI):m / z C 29 H 56 N3P2[M+H] + Calculated value: 508.3944; experimental value: 508.3936.

[0331] Synthesis of L3:

[0332]

[0333] 4.5g (12.1mmol, 1 equivalent) phosphonium salt 3 H2 is suspended in 50ml THF, and deprotonated by slowly adding 7.8mln-BuLi solution (1.55M in hexane, 12.1mmol, 1 equivalent), until a clear light yellow solution is formed. The solution is stirred 45 minutes, and then 2.67ml dicyclohexyl chlorophosphine (12.1mmol, 1 equivalent) is added at room temperature. Soon after the addition, a colorless solid precipitates. The suspension is stirred 2 hours, and then 7.8ml n-BuLi solution (1.55M in hexane, 12.1mmol, 1 equivalent) is slowly added, until a clear yellow solution is formed. The solution is stirred 30 minutes, and subsequently the solvent is removed in a vacuum. Residue is suspended in 50ml acetonitrile and stirred overnight to form a colorless solid. The solid was filtered off, washed with 2 x 20 ml acetonitrile and dried in vacuo to give L3 (4.26 g, 8.76 mmol, 72%) as a colorless solid.

[0334] 1 H NMR (400MHz, C6D6): δ = 7.33–7.27 (m, 4H, Ph 邻位 +Ph 间位 CH),7.04–6.97(m,1H,Ph 对位 CH),3.27(br,1H,P + Cy position 1CH), 2.78–2.54 (m, 4H, MeN(CH2)2NMe), 2.45 (d, J HH =8.9 Hz, 6H, NCH3), 2.33–2.22 (m, 2H, PCy2 position 2CH2), 2.17–1.96 (m, 6H, PCy2 position 1CH+ position 3CH2), 1.88–1.78 (m, 4H, P + Cy position 3CH2), 1.77–1.65 (m, 4H, PCy2 position 2CH2), 1.65–1.50 (m, 4H, P + Cy position 2 + position 4 CH2), 1.46–1.10 (m, 12H, P + Cy position 2 + PCy2 position 2 + position 3 + position 4 CH2). 13 C NMR (101MHz, C6D6): δ = 144.8 (dd, 2 J CP =5.6,3.3Hz,Ph 本位 C),129.6(s,Ph 间位 ),127.5(s,Ph 邻位 ),121.7(s,Ph 对位 ),48.0(d,2 J CP =5.1Hz,MeN(CH2)2NMe),37.8(dd, 1 J CP =90.8Hz, 3 J CP =18.0Hz,P + Cy position 1CH), 36.9 (dd, 1 J CP =13.5Hz, 3 J CP =8.1Hz,PCy2 position 1CH2),34.3(dd, 1 J CP =131.3,30.5Hz,P–C - –P),33.1(d, 2 J CP =6.3Hz,NCH3),32.7(d, 2 J CP =20.2Hz,P + Cy position 2CH2), 30.9(d, 3 J CP =8.8Hz,PCy2 position 3CH2),28.0(d, 3 J CP =7.7Hz,PCy2 position 3CH2),27.7(d, 3 J CP =12.5Hz,P + Cy position 3CH2), 27.1(s, PCy2 position 4CH2), 26.5(d, 2 J CP =14.0Hz,PCy2 position 2CH2),26.2(s,P + Cy position 4CH2). 31 PNMR (162MHz, C6D6): δ = 62.9 (d, 2 J PP =177.5Hz,P + Cy),-5.4(d, 2 J PP =178.0 Hz PCy2). IR (ATR) [cm -1]:3386(w),3069(w),2920(m),2843(w),1632(w),1587(w),1483(w),1443(w),1345(w),1226(m),1173(w),1116(w) ,1038(s),1000(w),945(w),915(m),850(w),758(w),703(vs),675(m),637(m),537(vs),500(vs),427(m),404(m). Melting point: 155.2℃. HRMS(ESI):m / z C 29 H 49 N2P2[M+H] + Calculated value: 487.3433; Exp. value: 487.3358

[0335] Synthesis of L4:

[0336]

[0337] 2.6g (7.3mmol, 1 equivalent) phosphonium salt 4 H2 is suspended in 30ml THF, and deprotonated by slowly adding 4.7mln-BuLi solution (1.55M in hexane, 7.3mmol, 1 equivalent), until a clear light yellow solution is formed. The solution is stirred 45 minutes, and then 1.61ml dicyclohexyl chlorophosphine (7.3mmol, 1 equivalent) is added at room temperature. Soon after the addition, a colorless solid precipitates. The suspension is stirred 2 hours, and then 4.7ml n-BuLi solution (1.55M in hexane, 7.3mmol, 1 equivalent) is slowly added, until a clear yellow solution is formed. The solution is stirred 30 minutes, and subsequently the solvent is removed in a vacuum. Residue is suspended in 30ml acetonitrile and stirred overnight to form a colorless solid. The solid was filtered off, washed with 2 x 10 ml acetonitrile and dried in vacuo to give L4 (2.22 g, 5.22 mmol, 72%) as a colorless solid.

[0338] 1 H NMR (400MHz, C6D6): δ = 3.06 (s, 1H, P + Cy position 1CH), 2.83–2.61 (m, 4H, MeN(CH2)2NMe), 2.52 (d, 3 J HP =9.1 Hz, 6H, NCH3), 2.27–2.16 (m, 2H, PCy2 position 3CH2), 2.13–2.03 (m, 4H, P +Cy position 2 + PCy2 position 2CH2), 2.02–1.85 (m, 6H, PCy2 position 1CH + PCy2 position 2 + position 3CH2), 1.80–1.74 (m, 2H, PCy2 position 4CHH2), 1.74–1.66 (m, 2H, P + Cy position 3CH2), 1.65–1.06 (m, 24H, P + Cy position 2 + position 3 + position 4 CH2 + PCy2 position 2 + position 3 + position 4 CH2). 13 CNMR (101MHz, C6D6): δ = 48.5 (d, 2 J CP =4.8Hz,MeN(CH2)2NMe),36.7(dd, 1 J CP =88.0Hz, 3 J CP =14.3Hz,P + Cy position 1CH), 35.6 (dd, 1 J CP =12.5Hz, 3 J CP =8.3Hz CH),33.6(d, 2 J CP =6.1Hz,NMe),32.9(d, 2 J CP =20.5Hz,PCy2 position 2CH2),31.6(d, 3 J CP =7.4Hz,PCy2 position 3CH2),28.7(dd, 2 J CP =6.3, 4 J CP =4.6Hz,P + Cy position 2CH2), 28.5(d, 3 J CP =6.6Hz,PCy2 position 3CH2),28.3(d, 2 J CP =12.8Hz,PCy2 position 2CH2),27.6(s,PCy2 position 4CH2),26.8(d, 3 J CP =13.7Hz,PCy2 position 3CH2),26.6(d, 4 J CP =1.8Hz,P + Cy position 4CH2), 17.0 (dd, 1 J CP=140.4,21.8Hz,P–C - –P),11.8(dd, 2 J CP =4.8,2.4Hz,P–C — CH3). 31 P NMR (162MHz, C6D6): δ = 68.6 (d, 2 J PP =172.0Hz,P + Cy),-2.9(d, 2 J PP =171.4Hz,PCy2). IR(ATR)[cm -1 ]:3389(w),2917(m),2844(s),1633(w),1444(w),1346(w),1234(w),1206(w),1165(s),1093(w ),1035(s),942(s),922(s),887(m),852(w),761(w),667(m),607(s),511(m),476(s),411(vs). Melting point: 122.0℃. HRMS(ESI):m / z C 24 H 47 N2P2[M+H] + Calculated value: 425.3209; experimental value: 425.3204.

[0339] Synthesis of L5:

[0340]

[0341] 1g (2.14mmol, 1 equivalent) phosphonium salt 5H2 is suspended in 10ml THF, and deprotonated by slowly adding 1.38mln-BuLi solution (1.55M in hexane, 2.14mmol, 1 equivalent), until a clear light yellow solution is formed. The solution is stirred 45 minutes, and then 0.47ml dicyclohexyl chlorophosphine (2.14mmol, 1 equivalent) is added at room temperature. Soon after the addition, a colorless solid precipitates. The suspension is stirred 2 hours, and then 1.38ml n-BuLi solution (1.55M in hexane, 2.14mmol, 1 equivalent) is slowly added, until a clear yellow solution is formed. The solution is stirred 30 minutes, and subsequently the solvent is removed in a vacuum. Residue is suspended in 30ml acetonitrile and stirred overnight to form a colorless solid. The solid was filtered off, washed with 2 x 15 ml acetonitrile and dried in vacuo to give L5 (1 g, 2.14 mmol, 87%) as a colorless solid.

[0342] 1 H NMR (400MHz, C6D6): δ = 3.10 (q, J HH =5.1Hz,12H,Pip position 1CH2),2.76(tdd, 3 J HP =13.8,11.2Hz,J HH =6.9Hz,1H,iPr CH3), 2.42–2.29(m,2H,Cy position 2CH2), 2.23–2.09(m,4H,Cy position 2CH2+position 1CH), 2.02–1.87(m,4H,Cy position 3CH2), 1.85–1.76(m,2H,Cy position 4CH2), 1.56–1.34(m,34H,Pip position 2+position 3CH2+Cy position 4CH2+iPr CH3). 13 C NMR (101MHz, C6D6): δ = 48.8 (d, 2 J CP =5.9Hz,Pip position 1CH2),37.8(dd, 1 J CP =31.4, 3 J CP =17.3Hz,Cy position 1CH),33.7(dd, 2 J CP =16.5, 4 J CP =10.0Hz,Cy position 2CH2),31.9(dd, 2 J CP =13.3,1.9Hz,iPr CH),30.0(dd, 1 J CP =177.3,29.3Hz,PC - -P),28.6(dd, 3 J CP =24.6,10.5Hz,Cy position 3CH2),27.7(s,Pip position 2CH2),27.0(d, 4 J CP =4.7Hz,Cy position 4CH2),26.3(d, 3 J CP =7.7Hz,iPr CH3),25.6(s,Pip position 3CH2). 31 P NMR (162MHz, C6D6): δ = 61.2 (d, 2 J PP =215.8Hz,P(Pip)3),-0.3(d, 2 JPP =215.9Hz,PCy2). IR(ATR)[cm -1 ]:3676(w),3399(w),2914(w),2839(w),1637(w),1437(w),1324(w),1204(w),1153(w),111 0(w),1041(w),1021(w),938(vs),850(w),695(w),664(w),592(w),553(w),530(w),462(w). Melting point: 143.0℃ (decomposition). HRMS(ESI):m / z C 31 H 60 N3P2[M+H] + Calculated value: 536.4257; experimental value: 536.4253.

[0343] Synthesis of L6:

[0344]

[0345] 1.92g (4.36mmol, 1 equivalent) phosphonium salt 2 H2 is suspended in THF and deprotonated by slowly adding 2.81ml n-BuLi solution (1.55M in hexane, 4.36mmol, 1 equivalent) until a clear light yellow solution is formed. The solution is stirred for 45 minutes, and then 0.43ml di-tert-butyl chlorophosphine (2.18mmol, 0.5 equivalent) is added at room temperature. The solution is stirred under reflux for 16 hours, during which time the phosphonium salt that is re-formed is a white solid precipitate. The solid is filtered out, and the solvent of the solution is removed in a vacuum. The residue is suspended in 20ml acetonitrile and stirred overnight to form a colorless solid. The solid is filtered out, washed with 2 × 15ml acetonitrile, and dried in a vacuum to obtain L6 (587mg, 1.29mmol, 59%) as a colorless solid.

[0346] 1 H NMR (400MHz, C6D6): δ = 3.04 (q, J HH =5.1Hz,12H,Pip position 1),1.98(dd, 3 J HP =15.4,3.0Hz,3H,PC - -CH3),1.53(d, 3 J HP =10.8Hz,18H, t Bu CH3), 1.30-1.45 (m, 18H, Pip position 2 + position 3 CH2). 13C NMR (101MHz, C6D6): δ = 47.9 (d, 2 J CP =4.8Hz,Pip position 1CH2),36.0(dd, 1 J CP =23.4Hz, 3 J CP =10.7Hz, t Bu C(CH3)3),33.0(d, 2 J CP =15.2Hz, t Bu C(CH3)3),27.1(d, 3 J CP =5.0Hz,Pip position 2CH2),25.5(d, 4 J CP =1.2Hz,Pip position 3CH2),17.5(d, 2 J CP =9.9Hz,PC - -CH3),16.9(dd, 1 J CP =191.5,25.3Hz,PC - -P). 31 P NMR (162MHz, C6D6): δ = 60.8 (d, 2 J PP =208.5Hz,P(Pip)3),25.3(d, 2 J PP =208.9Hz,P t Bu2). IR(ATR)[cm -1 ]:3998(w),3933(w),3903(w),3870(w),3802(w),3750(w),3388(w),2924(m),2848(w),1636(w),1439(w),1356(w), 1322(w),1258(w),1213(m),1153(s),1119(w),1052(vs),939(vs),888(s),854(m),808(m),696(m),587(m),545(m). Melting point: 147.8℃. HRMS(ESI):m / z C 25 H 52 N3P2[M+H] + Calculated value: 456.3631; experimental value: 456.3625.

[0347] Synthesis of L7:

[0348]

[0349] 6.5g (12.6mmol, 1 equivalent) phosphonium salt 7 H2 is suspended in 70ml THF, and deprotonated by slowly adding 8.4ml n-BuLi solution (1.5M in hexane, 12.6mmol, 1 equivalent), until a clear light yellow solution is formed. The solution is stirred 45 minutes, and then 3.34ml dicyclohexyl iodine phosphine (15.1mmol, 1.1 equivalent) is added at room temperature. Soon after the addition, a colorless solid precipitates. The suspension is stirred 2 hours, and then 8.4ml n-BuLi solution (1.5M in hexane, 12.6mmol, 1 equivalent) is slowly added, until a clear yellow solution is formed. The solution is stirred 30 minutes, and subsequently the solvent is removed in a vacuum. Residue is suspended in 75ml acetonitrile and stirred overnight to form a colorless solid. The solid was filtered off, washed with 5 x 15 ml acetonitrile and dried in vacuo to give L7 (5 g, 8.65 mmol, 69%) as a colorless solid.

[0350] 1 H NMR (400 MHz, C6D6): δ = 7.49–7.41 (m, 1H, toluene position 6CH), 7.31–7.26 (m, 1H, toluene position 4CH), 7.20–7.13 (m, 1H, toluene, position 3CH), 7.13–7.07 (m, 1H, toluene position 5CH), 2.94 (q, J HH =4.7Hz,12H,Pip position 1CH2),2.71(s,3H,tolueneCH3),2.53–2.45(m,2H,Cy position 2CH2),2.00–1.87(m,4H,Cy position 1CH+position 3CH2),1.78–1.71(m,4H,Cy position 4CH2),1.69–1.64(m,2H,Cy position 3CH2),1.59–1.30(m,28H,Pip position 2+Pip position 3+Cy position 2+Cy position 3CH2). 13 C NMR (101MHz, C6D6): δ = 143.3 (dd, 2 J CP =12.7,2.7Hz,toluene position 1C),142.0(d, 3 J CP =8.0Hz, toluene position 2C), 138.2(d, 3 J CP =5.6Hz, toluene position 6CH), 130.3(s, toluene position 4CH), 124.7(d, 4 J CP=2.7Hz, toluene position 3CH), 124.6(d, 4 J CP =2.4Hz, toluene position 5CH), 47.9(d, 2 J CP =3.8Hz,Pip position 1CH2),39.0(dd, 1 J CP =16.1Hz, 3 J CP =7.9Hz,Cy position 1CH),34.7(d, 2 J CP =22.4Hz,Cy position 2CH2),30.8(d, 3 J CP =7.3Hz,Cy position 3CH2),30.0(dd, 1 J CP =186.6,28.5Hz,PC - -P),29.1(d, 3 J CP =13.6Hz,Cy position 3CH2),27.5(s,Cy position 4CH2),26.8(d, 3 J CP =5.4 Hz, Pip position 2 CH2), 25.5 (s, Pip position 3 CH2), 22.9 (s, toluene CH3). 31 P NMR (162MHz, C6D6): δ = 51.6 (d, 2 J PP =160.3Hz,P(Pip)3),-1.3(d, 2 J PP =160.0Hz,PCy2). IR(ATR)[cm -1 ]:2924(m),2843(m),1590(w),1476(w),1442(w),1371(w),1328(w),1208(m),1154(w),1116(m),1057(s ),1015(m),939(vs),899(w),852(w),787(w),733(w),696(w),583(w),549(m),508(w),471(m),414(m). Melting point: 151.7℃ (decomposition). HRMS(ESI):m / zC 35 H 60 N3P2[M+H] + Calculated value: 584.4257; experimental value: 584.4249.

[0351] Synthesis of L8:

[0352]

[0353] 3.8g (8.64mmol, 1 equivalent) phosphonium salt 2 H2 is suspended in 25ml THF and deprotonated by slowly adding 5.72ml n-BuLi solution (1.51M in hexane, 8.64mmol, 1 equivalent) until a clear light yellow solution is formed. The solution is stirred for 45 minutes, and then a solution of 1.5g diadamantyl chlorophosphine (4.32mmol, 0.5 equivalent) in 10ml THF is added at room temperature. The solution is stirred under reflux for 16 hours, during which time the re-formed phosphonium salt precipitates as a white solid. The solid is filtered out, and the solvent of the solution is removed in a vacuum. The residue is suspended in 25ml acetonitrile and stirred overnight to form a colorless solid. The solid is filtered out, washed with 2×15ml acetonitrile, and dried in a vacuum to obtain L8 (1.87g, 4.32mmol, 71%) as a colorless solid.

[0354] IR(ATR)[cm 1 ]:2898(m),2844(w),2673(w),1447(w),1368(w),1325(w),1258(w),1213(w),1154(w),111 8(w),1058(m),1024(w),933(vs),884(m),809(w),693(m),667(w),558(w),466(m),423(m). Melting point: 179.9°C (decomposition).

[0355] Synthesis of L9:

[0356]

[0357] 3.0g (5.82mmol, 1 equivalent) phosphonium salt 7 H2 is suspended in 20ml THF, and deprotonated by slowly adding 3.88ml n-BuLi solution (1.6M in hexane, 5.82mmol, 1 equivalent), until a clear light yellow solution is formed. The solution is stirred for 45 minutes, and then 1.02ml diisopropyl iodide phosphine (6.4mmol, 1.1 equivalents) is added at room temperature. Soon after the addition, a colorless solid precipitates. The suspension is stirred for 2 hours, and then 3.88ml n-BuLi solution (1.6M in hexane, 5.82mmol, 1 equivalent) is slowly added, until a clear yellow solution is formed. The solution is stirred for 30 minutes, and subsequently the solvent is removed in a vacuum, until approximately 3ml remains. 40ml acetonitrile is added to the residue, and it is stirred overnight to form a colorless solid. The solid was filtered off, washed with 5 x 5 ml acetonitrile and dried in vacuo to give L9 (1.71 g, 3.39 mmol, 59%) as a colorless solid.

[0358] General procedure for the synthesis of L10-L17:

[0359] Phosphonium salt (1 equivalent) is suspended in THF (75ml). A solution of n-BuLi in hexane (1.6M, 1 equivalent) is slowly added. After the solution is stirred at room temperature for 1 hour, pentane (75ml) containing dialkyl iodide phosphine (1.2 equivalents) is added. The reaction mixture is stirred for 2 hours, and the colorless precipitate formed is filtered out and washed with pentane (3×20ml). The solid is dried in a vacuum, KOtBu (1.5 equivalents) is added, and the mixture is stirred overnight in toluene (100ml). The solvent is removed in a vacuum, and the residue is resuspended in pentane (200ml). The mixture is filtered with a diatomaceous earth plug, and the residue is extracted with pentane (3×50ml). The solvent is removed in a vacuum, and the residue is stirred in acetonitrile (150ml) until a finely dispersed colorless solid is obtained. The colorless solid is filtered out and washed with acetonitrile (3×50ml) to obtain the product.

[0360] Synthesis of L10:

[0361]

[0362] Phosphine L10 was synthesized from 10·H2 (2.02 g, 4.67 mmol) according to the general procedure for P,N-YPhos ligands. Colorless crystals suitable for single crystal X-ray diffraction experiments were obtained by slow evaporation of a saturated benzene solution.

[0363] Yield: (1.25 g, 2.50 mmol, 54%).

[0364] <h2 style=";text-align:left;direction:ltr"> 1 <h2 style=";text-align:left;direction:ltr"> H NMR(400MHz,C6D6):δ=7.37(d,<h2 style=";text-align:left;direction:ltr"> 3 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> HH <h2 style=";text-align:left;direction:ltr"> =7.6Hz,1H,oTol<h2 style=";text-align:left;direction:ltr"> 邻位 <h2 style=";text-align:left;direction:ltr"> ),7.25(d,<h2 style=";text-align:left;direction:ltr"> 3 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> HH <h2 style=";text-align:left;direction:ltr"> =7.4Hz,1H,oTol<h2 style=";text-align:left;direction:ltr"> 间位 <h2 style=";text-align:left;direction:ltr"> ),7.14–7.04(m,2H,oTol<h2 style=";text-align:left;direction:ltr"> 间位'+对位 <h2 style=";text-align:left;direction:ltr"> ),2.80–2.67(m,3H,NC2H4N+Cy,H1),2.67–2.62(m,5H,NC2H4N+CH3),2.50(d,<h2 style=";text-align:left;direction:ltr"> 3 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> HP <h2 style=";text-align:left;direction:ltr"> (8.9 Hz, 6H, NCH3), 2.38–2.26 (m, 2H, Cy, H2), 2.01–1.82 (m, 6H, PCy2, H1+2+3), 1.81–1.67 (m, 6H, PCy2, H3+4+Cy, H3), 1.67–1.59 (m, 2H, PCy2, H2), 1.59–1.25 (m, 11H, Cy, H2+3+4, PCy2, H2+3+4), 1.18–1.01 (m, 5H, Cy, H4, PCy2, H2+3+4) ppm.<h2 style=";text-align:left;direction:ltr"> 13 <h2 style=";text-align:left;direction:ltr"> C{<h2 style=";text-align:left;direction:ltr"> 1 <h2 style=";text-align:left;direction:ltr"> H}NMR(101MHz,C6D6):δ=142.6(dd,<h2 style=";text-align:left;direction:ltr"> 2 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> CP <h2 style=";text-align:left;direction:ltr"> =9.7,4.3Hz,oTol<h2 style=";text-align:left;direction:ltr"> 本位 <h2 style=";text-align:left;direction:ltr"> ),140.4(d,<h2 style=";text-align:left;direction:ltr"> 3 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> CP <h2 style=";text-align:left;direction:ltr"> <7.0Hz, oTol<h2 style=";text-align:left;direction:ltr"> 邻位 <h2 style=";text-align:left;direction:ltr"> ),137.2(d,<h2 style=";text-align:left;direction:ltr"> 3 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> CP <h2 style=";text-align:left;direction:ltr"> <6.8Hz, oTol<h2 style=";text-align:left;direction:ltr"> 邻位' <h2 style=";text-align:left;direction:ltr"> ),130.6(d,<h2 style=";text-align:left;direction:ltr"> 4 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> CP <h2 style=";text-align:left;direction:ltr"> <1.7Hz, oTol<h2 style=";text-align:left;direction:ltr"> 间位 <h2 style=";text-align:left;direction:ltr"> ),124.9(t,J=2.4Hz,oTol<h2 style=";text-align:left;direction:ltr"> 间位 <h2 style=";text-align:left;direction:ltr"> +<h2 style=";text-align:left;direction:ltr"> 对位 <h2 style=";text-align:left;direction:ltr"> ),48.5(d,<h2 style=";text-align:left;direction:ltr"> 2 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> CP <h2 style=";text-align:left;direction:ltr"> (4.7Hz,NC2H4N),39.0(dd,<h2 style=";text-align:left;direction:ltr"> 1 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> CP <h2 style=";text-align:left;direction:ltr"> =85.6,<h2 style=";text-align:left;direction:ltr"> 3 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> CP <h2 style=";text-align:left;direction:ltr"> =13.8Hz,Cy,C1),37.2(brs,PCy2,C1),34.0(dd,<h2 style=";text-align:left;direction:ltr"> 1 <h2 style=";text-align:left;direction:ltr"> JCP =134.3,31.8Hz,PCP),33.9(d, 2 J CP =6.0Hz,NCH3),32.8(d, 2 J CP =18.6Hz,Cy,C2),30.9(d, 3 J CP =9.6Hz,PCy2,C3),28.7–28.4(m,PCy2,C2+3),28.2(d, 3 J CP =7.8Hz,Cy,C3),27.5(s,PCy2,C4),27.2(d, 2 J CP =13.4Hz,PCy2,C2),26.7(d, 4 J CP =1.5Hz, Cy, C4), 22.6 (s, CH3, oTol) ppm. 31 P{ 1 H}NMR (162MHz, C6D6): δ = 57.8 (d, 2 J PP =161.3Hz,PCy(MeNC2H4NMe)),-1.9(d, 2 J PP =161.3Hz,PCy2)ppm. IR(ATR):2919(s),2844(s),1445(m),1236(m),1163(m),1108(w),1023(s),996(m),940(s), 911(m),886(m),849(m),728(s),679(m),665(m),634(w),544(m),488(m),468(m),430(w)cm -1 Melting point: 121°C 30 H 50 Elemental analysis of N2P2: Calculated values: C 71.97; H 10.07; N 5.59, Found values: C 72.06; H 10.29; N 5.56.

[0365] Synthesis of L11:

[0366]

[0367] Phosphine L11 was synthesized from 11·H2 (12.25 g, 25.1 mmol) according to the general procedure for P,N-YPhos ligands. Colorless crystals suitable for single crystal X-ray diffraction experiments were obtained by slow evaporation of a saturated benzene solution.

[0368] Yield: (12.4 g, 22.2 mmol, 88%).

[0369] NMR spectroscopy was performed at 70°C. 1 H NMR (400MHz, C6D6): δ = 7.36 (d, 3 J HH =7.5Hz,1H,oTol 邻位 ),7.13(d, 3 J HH =6.4Hz,1H,oTol 间位 ),7.06–6.93(m,2H,oTol 间位'+对位 ),3.85–3.71(m,2H,NCH(CH3)2),2.85–2.62(m,5H,NC2H4N+Cy,H1),2.57(s,3H,CH3,oTol),2.40–2.30(m, 2H,Cy,H2),2.19(s,2H,Cy,H2),1.95–1.81(m,4H,Cy,H3+PCy2,H1),1.73–1.06(m,24H,Cy+PCy2),1.01(d, 3 J HH =6.6Hz,6H,CH3,iPr),0.90–0.75(m,6H,CH3,iPr)ppm. 13 C{ 1 H}NMR (101MHz, C6D6): δ = 143.9 (dd, 2 J CP =6.7,3.4Hz,oTol 本位 ),140.7(d, 3 J CP =9.8Hz,oTol 邻位 ),136.0(d, 3 J CP =7.3Hz,oTol 邻位' ),130.6(s,oTol 对位 ),124.8(d, 4 J CP =1.5Hz,oTol 间位 ),124.4(d, 4 J CP =2.0Hz,oTol 间位' ),43.9(dd, 2 J CP =7.1Hz, 4 J CP= 2.2 Hz, NCH(CH3)2), 40.2 (dd, 1 J CP = 88.9 Hz, 3 J CP = 12.8 Hz, Cy, C1), 39.2 (brs, PCy2, C1), 38.8 (d, 2 J CP = 6.1 Hz, NC2H4N), 34.6 (dd, 1 J CP = 122.4, 31.1 Hz, PCP), 34.6 (d, 2 J CP = 22.9 Hz, Cy, C2), 30.9 (d, 3 J CP = 6.8 Hz, PCy2, C3), 29.1–28.8 (m, PCy2, C2+3), 28.3 (d, 3 J CP = 5.9 Hz, Cy, C3), 27.6–27.4 (m, PCy2, C2+4), 27.0 (d, 4 J CP = 1.6 Hz, Cy, C4), 22.2 (s, CH3, oTol), 21.6 (d, 3 J CP = 2.4 Hz, CH3, iPr), 21.1 (d, 3 J CP = 3.6 Hz, CH3, iPr) ppm. 31 P{ 1 H} NMR (162 MHz, C6D6): δ = 59.5 (d, 2 J PP = 168.2 Hz, PCy(iPrNC2H4NiPr)), 0.8 (d, 2 J PP = 168.2 Hz, PCy2) ppm. IR (ATR): 2913 (s), 2846 (m), 1447 (w), 1363 (w), 1213 (w), 1175 (m), 1102 (m), 1057 (s), 1011 (m), 992 (m), 900 (m), 883 (m), 849 (w), 726 (s), 683 (w), 577 (w), 545 (s), 535 (w), 509 (s), 465 (w) cm -1 . Melting point: 174 °C. C 34 H 58Elemental analysis of N2P2: Calculated values: C 73.34; H 10.50; N 5.03, Found values: C 72.98; H 10.67; N 4.96.

[0370] Synthesis of L12:

[0371]

[0372] Phosphine L12 was synthesized from 12·H2 (8.23 g, 15.1 mmol) according to the general procedure for P,N-YPhos ligands. Colorless crystals suitable for single crystal X-ray diffraction experiments were obtained by slow evaporation of a saturated hexane solution.

[0373] Yield: (7.51 g, 12.25 mmol, 81%).

[0374] NMR spectroscopy was performed at 70°C. 1 H NMR (400MHz, C6D6): δ = 7.42 (d, 3 J HH =7.5Hz,1H,oTol 邻位 ),7.20(d, 3 J HH =7.4Hz,1H,oTol 间位 ),7.09(t, 3 J HH =7.2Hz,1H,oTol 间位' ),7.03(t, 3 J HH =7.3Hz,1H,oTol 对位 ),3.31–3.17(m,2H,NCH2),3.02–2.83(m,6H,NCH2+NC2H4N),2.67(s,4H,CH3,oTol+Cy,H1),2.42–2.34(m,2H,Cy, H2),2.06–1.85(m,6H,PCy2,H1+2),1.78–1.61(m,8H,Cy,H3+PCy2,H2+3),1.60–1.06(m,22H,Cy / PCy2),0.94(dd, 3 J HH =6.6,2.7Hz,12H,CH3,iPen)ppm. 13 C{ 1 H}NMR (101MHz, C6D6): δ = 143.2 (dd, 2 J CP =10.8,3.8Hz,oTol 本位 ),140.5(d,3 J CP =8.0Hz,oTol 邻位 ),137.0(d, 3 J CP =6.8Hz,oTol 邻位' ),130.66(d, 4 J CP =0.9Hz,oTol 间位 ),125.1(d, 4 J CP =1.7Hz,oTol 间位' ),124.8(d, 5 J CP =2.3Hz,oTol 对位 ),46.1(dd, 2 J CP =4.8Hz, 4 J CP =1.2Hz,NCH2),45.8(dd, 2 J CP =5.2Hz, 4 J CP =1.9Hz,NC2H4N),40.20(dd, 1 J CP =86.3Hz, 3 J CP =12.7Hz,Cy,C1),38.6(d, 3 J CP =5.4Hz,CH2,iPen),38.1(dd, 1 J CP =15.5Hz, 3 J CP =8.1Hz,PCy2,C1),35.5(dd, 1 J CP =130.3,31.4Hz,PCP),33.9(d, 2 J CP =21.5Hz,Cy,C2),31.0(d, 3 J CP =8.1Hz,PCy2,C3),28.9–28.6(m,PCy2,C2+3),28.2(d, 3 J CP =6.7Hz,Cy,C3),27.6–27.3(m,PCy2,C2+4),27.2(s,CH(CH3)2),26.9(d, 4 J CP=1.6Hz,Cy,C4),23.0(s,CH3,iPen),22.8(s,CH3,iPen),22.5(s,CH3,oTol)ppm. 31 P{ 1 H}NMR (162MHz, C6D6): δ = 59.9 (d, 2 J PP =157.2Hz,PCy(iPenNC2H4NiPen)),-0.4(d, 2 J PP =157.2Hz,PCy2)ppm. IR(ATR):2918(s),2844(m),1442(w),1235(m),1148(s),1122(w),1063(s),1019(s) ,993(w),931(w),899(m),884(m),852(m),752(w),722(s),550(w),538(m),465(m)cm -1 Melting point: 140°C 38 H 66 Elemental analysis of N2P2: Calculated values: C 74.47; H 10.85; N 4.57, Found values: C 74.62; H 11.23; N 4.54.

[0375] Synthesis of L13:

[0376]

[0377] Phosphine L13 was synthesized from 13·H2 (10.8 g, 23.1 mmol) according to the general procedure for P,N-YPhos ligands. Colorless crystals suitable for single crystal X-ray diffraction experiments were obtained by slow evaporation of a saturated hexane solution.

[0378] Yield: (8.35 g, 15.6 mmol, 67%).

[0379] 1 H NMR (400MHz, C6D6): δ = 3.18 (dd, 3 J HP =13.8, 5 J HP =7.4Hz,2H,NCH2tBu),2.98–2.89(m,2H,NC2H4N),2.84–2.76(m,2H,NC2H4N),2.68(dd, 3 J HP =13.7, 5 J HP=5.2Hz,2H,NCH2),2.64–2.52(m,3H,Cy,H1+3),2.28–2.21(m,2H,PCy2,H3),2.11–1.85(m,8H,PCy2,H1+2+3),1.80–1.71(m,4H,PCy2,H2+4),1.68–1.57(m,3H,Cy,H4+PCy2,H3),1.53(dd, 3 J HP =16.0,3.0Hz,3H,PCPCH3),1.50–1.14(m,13H,Cy,H3+PCy2,H2+3+4),1.00(s,18H,CH3)ppm。 13 C{ 1 H}NMR(101MHz,C6D6):δ=60.1(d, 2 J CP =4.4Hz,NCH2tBu),49.1(d, 2 J CP =5.6Hz,NC2H4N),38.9(dd, 1 J CP =87.3, 3 J CP =8.8Hz,Cy,C1),35.7(dd, 1 J CP =13.2, 3 J CP =8.1Hz,PCy2,C1),33.6(d, 3 J CP =6.4Hz,C(CH3)3),32.8(d, 2 J CP =19.3Hz,Cy,C2),32.1(d, 3 J CP =8.8Hz,PCy2,C3),29.6–29.2(m,C(CH3)3+Cy,C3),28.4(d, 3 J CP =7.1Hz,PCy2,C3'),28.2(d, 2 J CP =12.2Hz,PCy2,C2),27.6(s,PCy2,C4),27.1(d, 2 J CP =13.7Hz,PCy2,C2'),27.0(d, 4 J CP =1.5Hz,Cy,C4),17.2(dd, 1 J CP=140.1, 3 J CP =24.2Hz,PCP),12.7(dd, 1 J CP =4.4, 3 J CP =1.5Hz,PCPCH3)ppm. 31 P{ 1 H}NMR (162MHz, C6D6): δ = 79.3 (d, 2 J PP =167.4Hz,PCy(newPenNC2H4NnewPen)),-3.9(d, 2 J PP =167.4Hz,PCy2)ppm. IR(ATR):2917(s),2845(s),1443(m),1168(m),1140(m),1067(m),1030(w),919(s),878(s),850(m),729(m),567(s),496(m),414(s)cm -1 Melting point: 144°C 32 H 62 Elemental analysis of N2P2: Calculated values: C 71.60; H 11.64; N 5.22, Found values: C 71.46; H 11.85; N 5.18.

[0380] Synthesis of L14:

[0381]

[0382] Phosphine L14 was synthesized from 14·H2 (4.01 g, 7.11 mmol) according to the general procedure for P,N-YPhos ligands. Colorless crystals suitable for single crystal X-ray diffraction experiments were obtained by slow evaporation of a saturated benzene solution.

[0383] Yield (2.13 g, 3.85 mmol, 54%).

[0384] NMR spectroscopy was performed at 70°C. 1 H NMR (400MHz, C6D6): δ = 6.82 (s, 2H, Mes 间位 ),6.79(s,2H,Mes 间位' ),3.46–3.36(m,2H,NC2H4N),3.30–3.24(m,2H,NC2H4N'),3.00–2.87(m,1H,Cy,H1),2.57(s,6H,CH3,Mes 邻位),2.48(s,6H,CH3,Mes 邻位 '),2.33–2.18(m,2H,Cy,H2),2.10(s,6H,CH3,Mes 对位 ),2.07–1.94(m,4H,Cy,H2+CH(CH3)2),1.78(dd, 3 J HP =16.9,2.8Hz,3H,PCPCH3),1.70–1.54(m,3H,Cy,H3+4),1.34–1.22(m,3H,Cy,H3+4),1.15(dd, 3 J HP =13.0Hz, 3 J HH =7.0Hz,6H,CH3,iPr),1.07(dd, 3 J HP =12.4Hz, 3 J HH =7.1Hz,6H,CH3,iPr)ppm。 13 C{ 1 H}NMR(101MHz,C6D6):δ=139.9(d, 2 J CP =5.4Hz,Mes 本位 ),138.8(d, 3 J CP =1.5Hz,Mes 邻位 ),138.4(d, 3 J CP =2.0Hz,Mes 邻位' ),135.9(s,Mes 对位 ),130.3(s,Mes 间位 ),130.1(s,Mes 间位' ),49.8(d, 2 J CP =7.3Hz,NC2H4N),44.9(dd, 1 J CP =87.2Hz, 3 J CP =7.4Hz,Cy,C1),29.8(dd, 2 J CP =16.7Hz, 4 J CP =4.7Hz,Cy,C2),28.1(d, 3 J CP =13.8Hz,Cy,C3),26.7(d, 4 JCP =1.8Hz,Cy,C4),26.48(dd, 1 J CP =140.1,31.2Hz,PCP),24.7(dd, 1 J CP =15.1Hz, 3 J CP =9.1Hz,CH(CH3)2),21.9(d, 2 J CP =15.1Hz,CH3,iPr),21.5(d, 2 J CP =17.9Hz,CH3,iPr),21.0(s.CH3,Mes ortho ),20.7(s.CH3,Mes para ),20.4(s,CH3,Mes 邻位' ),15.7(d, 1 J CP =3.0Hz,PCPCH3)ppm. 31 P{ 1 H}NMR (162MHz, C6D6): δ = 50.2 (d, 2 J PP =176.3Hz,PCy(MesNC2H4NMes)),8.3(d, 2 J PP =176.3Hz,PiPr2)ppm. IR(ATR):2915(m),2847(w),1450(m),1235(m),1216(m),1189(m),1153(m),1073(s) ,958(m),913(s),873(s),846(s),823(s),622(m),554(m),533(w),444(m),436(m)cm -1 Melting point: 177°C 34 H 54 Elemental analysis of N2P2: Calculated values: C 73.88; H 9.85; N 5.07, Found values: C 73.52; H 9.85; N 4.91.

[0385] Synthesis of L15:

[0386]

[0387] Phosphine L15 was synthesized from 15·H2 (6.51 g, 13.4 mmol) according to the general procedure for P,N-YPhos ligands, except that the phosphonium salt was deprotonated in toluene. Colorless crystals suitable for single-crystal X-ray diffraction experiments were obtained by slow evaporation of the saturated hexane solution.

[0388] Yield: (4.93 mg, 8.88 mmol, 66%).

[0389] NMR spectroscopy was performed at 70° C. In some cases, NMR spectral assignment was not possible due to overlapping peaks from three different cyclohexyl moieties. 1 H NMR (400MHz, C6D6): δ = 7.42 (d, 3 J HH =7.4Hz,1H,oTol 邻位 ),7.24–7.20(m,1H,oTol 间位 ),7.11–7.01(m,2H,oTol 间位'+对位 ),2.67(s,3H,CH3,oTol),2.61–2.51(m,7H,CH3,DMCDA+Cy,H1),2.47–2.12(m,5H,PCy2+Cy(NCH3)2+Cy),1.88–0.95(m,37H,PCy2+Cy(NCH3)2+Cy)ppm. 13 C{ 1 H}NMR (101MHz, C6D6): δ = 142.7 (bs, oTol 本位 ),140.9(d, 3 J CP =7.4Hz,oTol 邻位 ),137.9(d, 3 J CP =6.2Hz,oTol 邻位' ),130.6(d, 4 J CP =1.7Hz,oTol 间位 ),125.0(d, 4 J CP =2.5Hz,oTol 间位' ),124.8(d, 5 J CP =2.0Hz,oTol 对位 ),66.0(s,Cy(NCH3)2,C1),64.5(d, 2 J CP =4.1Hz,Cy(NCH3)2,C1),39.3(dd, 1 JCP =82.1Hz, 3 J CP =13.7Hz,Cy,C1+PCy2,C1),36.2(PCy2,C1),35.1(dd, 1 J CP =132.8,33.1Hz,PCP),33.4(s,Cy(NCH3)2+Cy+PCy2),32.7(d,J=18.2Hz,Cy(NCH3)2+Cy+PCy2),32.0(s,NCH3),31.4(d,J=12.7Hz,Cy(NCH3) 2+ Cy+PCy2),30.5(d,J=6.0Hz,Cy(NCH3)2+Cy+PCy2),30.0(t,J=4.1Hz,Cy(NCH3)2+Cy+PCy2),29.9(d,J=7.3Hz,Cy(NCH3)2+Cy+PCy2),29.5(d, 2 J CP =5.8Hz,NCH3),29.2–28.9(m,Cy(NCH3)2+Cy+PCy2),28.6(d,J=6.5Hz,Cy(NCH3)2+Cy+PCy2),28.1(dd,J=31.1,9.9Hz,Cy(NCH3)2+Cy+PCy2),2 7.8–27.3(m,Cy(NCH3)2+Cy+PCy2), 26.8(d,J=1.5Hz,Cy(NCH3)2+Cy+PCy2), 24.9(d,J=18.6Hz, Cy(NCH3)2+Cy+PCy2), 22.8(s,CH3,oTol)ppm. 31 P{ 1 H}NMR (162MHz, C6D6): δ = 59.4 (d, 2 J PP =152.2Hz,PCyDMCDA),-0.6(bq,PCy2)ppm. IR(ATR):2912(s),2848(m),1442(m),1218(m),1185(s),1058(m),1011 (s),913(m),884(m),845(m),726(s),702(m),548(m),489(s),469(m)cm -1 Melting point: 145°C 34 H 56 Elemental analysis of N2P2: Calculated values: C 73.61; H 10.17; N 5.05, Found values: C 73.74; H 10.43; N 5.05.

[0390] Synthesis of L16:

[0391]

[0392] Phosphine L16 was synthesized from 16·H2 (1.44 g, 2.76 mmol) according to the general procedure for P,N-YPhos ligands, except that filtration through a plug of celite was performed in toluene due to lack of solubility in pentane. Colorless crystals suitable for single crystal X-ray diffraction experiments were obtained by slow evaporation of a saturated benzene solution.

[0393] Yield: (1.14 g, 1.93 mmol, 70%).

[0394] 1 H NMR (400MHz, C6D6): δ = 7.25 (d, 3 J HH =7.4Hz,1H,oTol 对位 ),7.20(d, 3 J HH =7.0Hz,1H,oTol 邻位 ),7.13–7.03(m,2H,oTol 邻位'+间位 ),3.37(t, 3 J HH =4.5Hz,12H,Mor,H2),2.85(q, 3 J HH =4.6Hz,12H,Mor,H3),2.54(s,3H,CH3),2.36–2.26(m,2H,Cy,H3),1.92–1.76(m,4H,Cy,H1+3 ),1.72–1.67(m,3H,Cy,H2+4),1.63–1.52(m,2H,Cy,H2),1.45–1.12(m,10H,Cy,H2+3+4)ppm. 13 C{ 1 H}NMR (101MHz, C6D6): δ = 142.2 (dd, 2 J CP =12.5,2.0Hz,oTol 本位 ),141.4(d, 5 J CP =8.0Hz,oTol 对位 ),137.4(d, 3 J CP =6.0Hz,oTol 邻位 ),130.7(d, 4 J CP =1.5Hz,oTol间位 ),125.1(dd, 3 J CP =5.2Hz, 4 J CP =2.5Hz,oTol 邻位'+间位' ),67.2(d, 2 J CP =5.8Hz,Mor,C2),47.4(d, 3 J CP =3.8Hz,Mor,C3),38.8(dd, 1 J CP =15.3Hz, 3 J CP =8.0Hz,Cy,C1),34.6(d, 3 J CP =21.9Hz,Cy,C3),30.7(d, 2 J CP =7.3Hz,Cy,C2),28.9(d, 3 J CP =13.8Hz,Cy,C3),28.2(d, 2 J CP =6.0Hz,Cy,C2),27.3(s,Cy,C4),22.7(s,CH3)ppm. 31 P{ 1 H}NMR (162MHz, C6D6): δ = 48.6 (d, 2 J PP =161.4Hz,P(Mor)3),-3.4(d, 2 J PP =161.4Hz,PCy2)ppm. IR(ATR):2915(w),2833(w),1250(m),1128(w),1110(s),1078(m),1006(w),990(w), 946(s),917(w),889(m),847(w),722(m),706(m),540(w),501(m),490(m),464(m)cm -1 . Melting point: 137℃ (decomposition). 32 H 53 Elemental analysis of N3O3P2: Calculated values: C 65.17; H 9.06; N 7.13, Found values: C 65.14; H 9.19; N 7.06.

[0395] Synthesis of L17:

[0396]

[0397] Phosphine L17 was synthesized from 17·H2 (1.21 g, 2.39 mmol) according to the general procedure for P,N-YPhos ligands, except that Cy2PI was added to pentane (20 ml). Excess THF was necessary to dissolve the in situ formed ylide. Filtration through a plug of Celite was performed in toluene. Colorless crystals suitable for single crystal X-ray diffraction experiments were obtained by slow evaporation of the saturated hexane solution.

[0398] Yield: (5.67 g, 10.4 mmol, 87%).

[0399] 1 H NMR (400MHz, C6D6): δ = 7.28 (d, 3 J HH =7.8Hz,6H,Ph 邻位 ),7.11(t, 3 J HH =7.9Hz,6H,Ph 间位 ),6.92(t, 3 J HH =7.4Hz,3H,Ph 对位 ),2.74(d, 3 J HP =7.8Hz,9H,CH3NPh),2.00–1.72(m,15H,PCy2,H1+2+3+4,PCPCH3),1.45–1.21(m,10H,PCy2,H2+3+4)ppm. 13 C{ 1 H}NMR (101MHz, C6D6): δ = 147.9 (d, 2 J CP =3.1Hz,Ph 本位 ),128.8(s,Ph 间位 ),127.0(t,J=2.5Hz,Ph 邻位 ),124.5(s,Ph 对位 ),40.9(t,J=3.9Hz,CH3NPh),36.0(dd, 1 J CP =14.6, 3 J CP =9.1Hz,PCy2,C1),32.5(d, 2 J CP =18.0Hz,PCy2,C2),31.8(d, 2 J CP=10.8Hz,PCy2,C2),28.8(d, 3 J CP =7.8Hz,PCy2,C3),28.3(d, 3 J CP =11.4Hz,PCy2,C3),27.5(s,PCy2,C4),19.3(dd, 1 J CP =202.8,22.7Hz,PCPCH3),15.8(d, 2 J CP =12.1Hz,PCPCH3)ppm. 31 P{ 1 H}NMR (162MHz, C6D6): δ = 53.4 (d, 2 J PP =193.3Hz,P(PhNMe)3),-3.3(d, 2 J PP =193.3Hz,PCy2)ppm. IR(ATR):2918(m),2840(w),1593(w),1489(m),1443(w),1269(m),1172(w),1053(m), 1025(m),908(m),879(s),777(w),759(m),692(s),547(m),519(m),497(w),456(w)cm -1 Melting point: 152°C 35 H 49 Elemental analysis of N3P2: Calculated values: C 73.27; H 8.61; N 7.32, Found values: C 73.59; H 9.01; N 7.06.

[0400] Synthesis of L18:

[0401]

[0402] Phosphine L18 was synthesized from 18·H2 (1.30 g, 2.69 mmol) according to the general procedure for P,N-YPhos ligands.

[0403] Yield: 1.25 g, 2.50 mmol, 54%.

[0404] 1 H NMR (400MHz, C6D6): δ = 7.49 (d, 3 J HH =7.7Hz,2H,CH 芳香族 ),7.20–7.11(m,4H,CH芳香族 ), 7.07–6.88 (m, 7H, CH 芳香族 ), 3.63 (tt, 3 J HH = 11.2, 5.9 Hz, 2H, CH2, bridge), 2.68 (dh, 2 J HP = 14.5, 3 J HH = 7.2 Hz, 2H), 2.48 (tt, 3 J HH = 11.0, 5.2 Hz, 2H, CH2, bridge), 2.42–2.33 (m, 2H, PCy2, H2), 1.92–1.84 (m, 2H, PCy2, H2), 1.74–1.62 (m, 4H, PCy2, H2+4), 1.54–1.31 (m, 14H, PCy2+CH3, iPr), 1.31–1.10 (m, 12H, PCy2+CH3, iPr) ppm. 13 C{ 1 H} NMR (101 MHz, C6D6): δ = 145.9 (d, J = 1.9 Hz, C 芳香族 ), 142.9 (d, J = 8.8 Hz, C 芳香族 ), 138.6 (d, J = 2.4 Hz, C 芳香族 ), 134.4 (d, J = 8.0 Hz, C 芳香族 ), 131.0 (s, C ar. ), 129.3 (s, C 芳香族 ), 127.6 (s, C 芳香族 ), 126.63 (s, C 芳香族 ), 126.43 (s, C 芳香族 ), 124.07 (d, J = 1.8 Hz, C 芳香族 ), 38.5 (dd, 1 J CP = 14.4 Hz, 1 J CP = 6.9 Hz, PCy2, C1), 34.4 (d, 2 J CP = 20.9 Hz, PCy2, C2), 32.1 (d, 4 J CP = 3.3 Hz, CH2, bridge), 30.9 (d, 3 J CP = 9.9 Hz, PCy2, C3), 30.6 (dd, 1 J CP= 122.9, 29.0 Hz, PCP), 30.3 (d, 1 J CP = 7.1 Hz, CH, iPr), 29.6 (d, 1 J CP = 7.1 Hz, CH, iPr), 28.7 (d, 2 J CP = 13.3 Hz, PCy2, C2), 28.1 (d, 3 J CP = 7.1 Hz, PCy2, C3), 27.5 (s, PCy2, C4), 20.7 (dd, 2 J CP = 7.1 Hz, 4 J CP = 3.4 Hz, CH3, iPr), 19.8 (dd, 2 J CP = 5.6 Hz, 4 J CP = 2.8 Hz, CH3, iPr) ppm. 31 P{ 1 H} NMR (162 MHz, C6D6): 50.88 (d, 2 J PP = 142.4 Hz, P(NR2)(iPr)2), -6.86 (d, 2 J PP = 142.6 Hz, PCy2) ppm. IR (ATR): 2919 (m), 2848 (w), 1481 (m), 1445 (w), 1282 (w), 1216 (m), 1072 (w), 1025 (w), 989 (m), 908 (m), 865 (w), 845 (w), 749 (s), 696 (s), 559 (s), 489 (w) cm -1 . Melting point: 160 °C.

[0405] General procedure for the palladium-catalyzed Buchwald-Hartwig amination of aryl chlorides:

[0406] 172mg (1.5mmol, 1 equivalent) potassium tert-butoxide is filled into the 5ml screw cap bottle in the glove box, and the bottle has the stirring rod and septum cover of Teflon coating. Bottle is taken out from glove box, and 4ml tetrahydrofuran, 0.118ml (1mmol, 1 equivalent) 4-chlorotoluene, 0.259ml tetradecane (1mmol, 1 equivalent) and 1.1mmol (1.1 equivalent) amine are added by syringe. Into the second bottle, be filled with the free ligand and tris (dibenzylideneacetone) dipalladium (0) of equimolar amount. Make catalyst preformed in 0.5ml THF, and stir 30 minutes. Catalyst solution is added in reaction mixture, and stir at room temperature or 60 ℃. Take out small aliquot, and filter through silica gel with ethyl acetate, and analyze by GC / MS and GC / FID.

[0407] General procedure for the coupling of 4-chloroanisole with n-BuLi and t-BuLi:

[0408] The reaction is carried out in a 5ml screw cap bottle, and the bottle has a stirring rod and a septum cap coated with Teflon. In a glove box, a palladium source (0.03mmol) and a part (0.03mmol) are added to the bottle. Then, the bottle is taken out from the glove box, and 4-chloroanisole (1mmol, 142.6mg) and toluene (1ml) are added and stirred for 30 minutes. It is 3.3ml that n-BuLi (1.6M in hexane, 1.2mmol, 0.75ml) is diluted to final volume with toluene, and at room temperature uses a syringe pump to add within 1 hour. The reaction is quenched by adding 0.1ml water. Take out a small aliquot, and filter through silica gel with ethyl acetate, and analyze by GC / MS and GC / FID.

[0409] General procedure for the coupling of 4-chlorotoluene with acetone:

[0410] Alkali is filled in the 5ml screw cap bottle in the glove box, and described bottle has stirring rod and the septum cap that Teflon applies.Bottle is taken out from glove box, and adds acetone (1mmol, 1 equivalent) and 0.259ml tetradecane (1mmol, 1 equivalent) by syringe.In second bottle, be filled into the free ligand and the palladium source of equimolar amount.Catalyst is preformed in 0.5mlTHF, and stirred 15 minutes.Then in reaction mixture, add catalyst solution and at room temperature stirred 16 hours.Take out little aliquot, and pass through silica gel filtration with ethyl acetate, and analyze by GC / MS and GC / FID.

[0411] General procedure for gold-catalyzed hydroamination:

[0412] 0.005mmol LAuCl and NaBAr FThe reaction was then filled into a 2 mL screw cap vial with a Teflon coated stirring bar and septum cap in the glove box. Amine (5.25 mmol) and alkyne (5.00 mmol) were added via syringe. The vial was heated on a hot plate to the indicated temperature while stirring. A small aliquot was removed via syringe and added directly to an NMR tube to monitor the reaction progress. 1 The yield was calculated by integrating the peak of the alkyne starting material relative to the peak of the imine product in the H-NMR spectrum.

[0413] General procedure for the hydrogenation of aryl chlorides:

[0414] In Schlenk tube, weigh 0.03mmol Pd (dba) , and add 2mL THF.Add 0.03mmol part subsequently, and make the reaction carry out 30 minutes, to produce active catalyst.In reaction mixture, add each in 1mmol halogenated compound and internal standard, and stir for 2 hours.Finally, add 0.05mmol sodium tetrafluoroborate and 1mmol potassium phosphate, and by three freeze-pump-thaw cycles, reaction vessel is degassed.After the third freeze-pump-thaw cycle, hydrogen is introduced in the reaction mixture, and after Schlenk tube is warmed to 23 ℃, pipe is sealed, and reaction mixture is vigorously stirred at 50 ℃.After 24 hours, reaction mixture is exposed in the air, diluted with ethyl acetate (3mL), and analyzed by GC or GCMS analysis aliquots.

[0415] General procedure for the coupling of 4-chlorotoluene with ammonia:

[0416] The reaction is carried out in a screw cap bottle with a septum plate cover. In a glove box, Pd2dba3 (0.0125mmolPd) and ligand (0.0125mmol) are added to the bottle. Next, THF (0.5ml) is added and the mixture is stirred for 30 minutes. In another bottle, KOtBu (57.3mg, 0.5mmol) is filled, and 4-chlorotoluene (31.6mg, 29.6μl, 0.25mmol), tetradecane (49.6mg, 6.47μl, 0.25mmol) and 1,4-dioxane (2.5ml) are added subsequently by a syringe outside the glove box. The catalyst stock solution is added to the bottle, followed by addition of ammoniacal dioxane (0.5M, 2ml, 1mmol), and the mixture is heated to 110°C in a temperature-controlled aluminum heating block for 5 hours. Take out a small aliquot, filter through silica gel with ethyl acetate as eluent, and analyze by GC-FID.

[0417] Results of the Buchwald-Hartwig amination

[0418] Table 1: Results of the Buchwald-Hartwig amination reaction:

[0419]

[0420] Condition A: 1 mmol ArCl, 1.1 equivalents amine, 1.5 equivalents KO t Bu, 0.5 mol% Pd and ligand, room temperature, THF; Condition B: 1 mmol ArCl, 1.1 equivalents amine, 1.5 equivalents KO t Bu, 1 mol% Pd and ligand, room temperature, THF; Condition C: 1 mmol ArCl, 1.1 equivalents amine, 1.5 equivalents KO t Bu, 0.5 mol% Pd and ligand, 50 °C, THF.

[0421] Arylation results of ammonia reactions

[0422]

[0423] Table 1: Ligand screening results for monoarylation of ammonia (1 mmol) with 4-chlorotoluene (0.25 mmol) in 1,4-dioxane using KOtBu (0.5 mmol) and L·Pd2dba3 (5 mol%) at 110°C. Yields are GC-FID yields after 5 h, using n-tetradecane as the internal standard and normalized to the sum of all peaks.

[0424]

[0425] Results of coupling of organolithium reagents with aryl chlorides

[0426]

[0427] Table 2: Results of coupling of organolithium reagents with aryl chlorides

[0428]

[0429] Reaction conditions: 1 mmol ArCl, 1.1 equivalents RLi, in toluene at room temperature. R-Li was added over a period of 1 hour. Yields were determined by calibrated GC analysis using tetradecane as an internal standard. a) Only isomerized products were observed.

[0430] Arylation results of acetone reaction:

[0431] Table 3: Screening of reaction conditions

[0432]

[0433]

[0434]

[0435] Reaction conditions: 1 mmol ArCl, room temperature, 16 hours. Yields were determined by calibrated GC analysis using tetradecane as an internal standard. a) No catalyst preformed, b) Preform with ArCl in THF for 15 min, c) Preformed with ArCl in THF for 1 hour, d) In THF without ArCl preformation for 15 min, e) In THF without preformation of ArCl, f) Wet technical grade acetone and react under air.

[0436] scope:

[0437]

[0438] Reaction conditions: 1 mmol ArCl, 3 equivalents Cs2CO3, in 3.7 ml acetone, 0.1 mol% [Pd(allyl)Cl]2, 0.2 mol% L7, room temperature, 16 hours, yield of isolated product.

[0439] Hydrogenation reaction results of aryl halides:

[0440]

[0441] Table 5: Hydrogenation results of aryl halides

[0442]

[0443] Reaction conditions: 1 mmol ArCl, 3 mol% Pd2dba3, 3 mol% L, 15 mol% NaBF4, 1 mmol K3PO4 in THF at 50°C or 60°C under 1 atm H2.

[0444] Synthesis and Characterization of Acetone Arylation Products :

[0445] 1-(4-(tert-Butyl)phenyl)propan-2-one (1)

[0446]

[0447] Compound 1 was synthesized according to the general procedure, purified by filtration over silica, and isolated as a colorless liquid in 99% yield. The analytical data were consistent with those reported in the literature.

[0448] 1H NMR (400MHz, CDCl3): δ7.36 (d, J = 8.27Hz, 2H), 7.14 (d, J = 8.29Hz, 2H), 3.66 (s, 2H), 2.16 (s, 3H), 1.32 (s, 9H). 13 C NMR (101MHz, CDCl3): δ=206.9,150.1,131.3,129.2,125.8,50.7,34.6,31.5,29.4. IR(cm -1 ):2961(m),2904(w),2869(w),1712(vs),1514(m),1463(w),1413(m),1362(m),1268 (m),1229(w),1158(m),1109(w),1020(w),836(w),687(w),593(w),547(m),421(w). MS (EI): m / z (%) = 190.1 (35.54, [M+]), 175.1 (53.75), 147.7 (100), 133.1 (37.95), 132.1 (30.79), 117.1 (35.9), 105.1 (23.26), 91.0 (21.26).

[0449] 1-(Naphthalen-1-yl)propan-2-one (2)

[0450]

[0451] Compound 2 was synthesized according to the general procedure, purified by filtration over silica, and isolated as a colorless liquid in 95% yield. The analytical data were consistent with those reported in the literature.

[0452] 1 H NMR (400MHz, CDCl3): δ7.88 (ddd, J=6.94, 4.73, 1.99Hz, 2H), 7.81 (d, J=8.13Hz, 1H), 7.52 (dd d,J=7.21,4.93,1.79Hz,2H),7.47–7.42(m,1H),7.41–7.36(m,1H),4.12(s,2H),2.12(s,3H). 13 C NMR (101MHz, CDCl3): δ=207.1,134.0,132.3,131.2,128.9,128.4,128.2,126.7,126.1,125.7,124.0,49.4,29.1. IR(cm -1):3046(w),2970(w),1708(vs),1596(m),1510(m),1397(m),1356(m), 1228(m),1163(m),1021(m),787(vs),560(w),530(m),451(w),427(w). MS (EI): m / z (%) = 115 (41.58), 139.1 (18.12), 141.1 (100), 142.1 (29.51), 184.1 (38.06 [M+]).

[0453] Ethyl 2-(2-oxopropyl)benzoate (3)

[0454]

[0455] Compound 3 was synthesized according to the general procedure, purified by column chromatography (hexane / ethyl acetate 20:1), and isolated as a colorless liquid in 91% yield. The analytical data were consistent with those reported in the literature. 1 H NMR (400MHz, CDCl3): δ = 7.9 (ddd, J = 6.9, 4.7, 2.0Hz, 2H), 7.8 (d, J = 8.1Hz, 1H), 7.5 (d dd,J=7.2,4.9,1.8Hz,2H),7.5–7.4(m,1H),7.4–7.4(m,1H),4.1(s,2H),2.1(s,3H). 13 C NMR (101MHz, CDCl3): δ=209.3,166.4,138.5,130.2,129.6,69.8,61.2,52.8,51.5,29.4,14.5. IR(cm -1 ):2974(w),2933(w),2770(w),1709(vs),1610(w),1576(w),1465(w),1417(w),1367(w),1275(vs ),1179(w),1105(m),1066(w),1022(w),914(w),856(w),760(w),710(w),506(w),468(w),402(w). MS (EI): m / z (%) = 89.0 (21.28), 90.0 (29.44), 91.0 (27.31), 107.0 (15.74), 11 8.0(26.5),135.0(28.79),136.0(62.39),161.0(25.21),164.1(100,[M+]).

[0456] 1-(4-Fluorophenyl)propan-2-one (4)

[0457]

[0458] Compound 4 was synthesized according to the general procedure, purified by filtration over silica, and isolated as a colorless liquid in 98% yield. The analytical data were consistent with those reported in the literature.

[0459] 1 H NMR (400MHz. CDCl3): δ7.16 (dd.J=8.48.5.45Hz.2H).7.02 (tJ=8.64Hz.2H).3.68 (s.2H).2.16 (s.3H). 19 F NMR (75MHz. CDCl3): δ=-114.6. IR(cm -1 ):3044(w).3002(w).2901(w).1712(s).1602(w).1508(vs).1418(w).1357(w).1326(w).1221(s ).1157(m).1096(w).1017(w).980(w).839(w).796(w).602(w).510(w).488(w).432(w).400(w). MS (EI): m / z (%) = 83.0 (26.44), 109.0 (100), 110.0 (24.15), 152.0 (26.45, [M+]).

[0460] 1-(2-Fluorophenyl)propan-2-one (5)

[0461]

[0462] Compound 5 was synthesized according to the general procedure, purified by column chromatography (hexane / ethyl acetate 20:1), and isolated as a colorless liquid in 85% yield. The analytical data were consistent with those reported in the literature. 1 H NMR(400MHz.CDCl3): δ7.30–7.23(m.1H).7.18(td.J=7.48.1.89Hz.1H).7.14–7.03(m.2H).3.74(s.2H).2.20(s.3H). 13 C NMR(101MHz.CDCl3)δ205.1.161.1(dJ=245.71Hz).131.8(dJ=4.21Hz).129.2(dJ=8.11Hz ).124.4(dJ=3.62Hz).121.8(dJ=16.19Hz).115.6(dJ=21.71Hz).44.0(dJ=2.31Hz).29.5.19 F NMR (75MHz. CDCl3): δ=-115.3. IR(cm -1 ):2999(w).2935(w).2835(w).1708(vs).1610(m).1578(w).1501(vs).1464(w).1424(w).1355(m).1302(w).12 52(vs).1217(w).1156(s).1117(w).1043(s).927(w).874(w).809(m).706(w).533(m).476(w).453(w).409(w). MS (EI): m / z (%) = 83.0 (33.63), 109.0 (100), 110.0 (26.82), 152.0 (42.04, [M+]).

[0463] 1-(3-(Methylthio)phenyl)propan-2-one(6)

[0464]

[0465] Compound 6 was synthesized according to the general procedure, purified by column chromatography (hexane / ethyl acetate 20:1), and isolated as a colorless liquid in 93% yield. The analytical data were consistent with those reported in the literature. 1 H NMR(400MHz.CDCl3): δ7.25(tJ=7.69Hz.1H).7.16(dt.J=8.16.1.47Hz.1H).7.09(dJ =1.83Hz.1H).6.97(dt.J=7.58.1.40Hz.1H).3.66(s.2H).2.48(s.2H).2.16(s.3H). 13 C NMR (101MHz.CDCl3): δ=206.2.139.3.135.0.129.3.127.5.126.3.125.3.51.0.29.5.15.9. IR(cm -1 ):2920(w).1710(vs).1591(m).1475(m).1421(m).1356(m).1321(m).1225(m) .1157(m).1086(m).969(w).881(w).770(s).701(s).526(m).467(w).438(w). MS (EI): m / z (%) = 108.0 (40.65), 112.0 (28.93), 125.0 (49.8), 158.0 (100), 160.0 (38.19, [M+]).

[0466] 1-Chloro-2-methylbenzene (7)

[0467]

[0468] Compound 7 was synthesized according to the general procedure, purified by column chromatography (hexane / ethyl acetate 20:1), and isolated as a colorless liquid in 73% yield. The analytical data were consistent with those reported in the literature. 1 H NMR(400MHz.CDCl3)δ7.22–7.16(m.3H).7.16–7.12(m.1H).3.71(s.2H).2.25(s.3H).2.14(s.3H). 13 C NMR (101MHz.CDCl3): δ=206.5.137.0.133.3.130.6.130.5.127.5.126.4.49.3.29.4.19.7. IR(cm -1 ):3064(w).3018(w).2918(w).1709(vs).1604(w).1495(w).1462(w).1420(w).1356(m).132 4(w).1227(w).1159(m).1110(w).1052(w).741(s).636(w).567(w).515(w).469(w).444(w). MS (EI): m / z (%) = 77.0 (23.66), 105.1 (100), 106.1 (31.36), 148.1 (38.81, [M+]).

[0469] 1-(5-Methoxy-2-methylphenyl)propan-2-one (8)

[0470]

[0471] Compound 8 was synthesized according to the general procedure, purified by column chromatography (hexane / ethyl acetate 20:1), and isolated as a colorless liquid in 60% yield. The analytical data were consistent with those reported in the literature. 1 H NMR (400MHz.CDCl3): δ=7.2–7.2(m.1H).7.2–7.1(m.0H).3.7(s.1H).2.3(s.1H).2.1(s.1H). MS (EI): m / z (%) = 91.0 (22.26), 135.1 (100), 136.1 (22.07), 178.1 (29.6, [M+]).

[0472] 1-(1-Methyl-1H-pyrrolo[2.3-b]pyridin-4-yl)propan-2-one (9)

[0473]

[0474] Compound 9 was synthesized according to the general procedure, purified by column chromatography (hexane / ethyl acetate 20:1), and isolated as a colorless liquid in 78% yield. 1 H NMR(400MHz.CDCl3): δ8.30(dJ=4.84Hz.1H).7.19(dJ=3.46Hz.1H).6.92(dJ =4.83Hz.1H).6.44(dJ=3.44Hz.1H).3.94(s.2H).3.89(s.3H).2.14(s.3H). 13 C NMR (101MHz.CDCl3): δ205.1.147.9.143.2.135.5.129.3.120.7.116.7.97.8.48.6.31.6.29.4. IR(cm -1 ):3049(w).2913(w).1712(vs).1585(m).1514(s).1436(w).1406(m).1348(s).1299(m).1210(w).1159(w).1 087(w).1030(w).1010(w).965(w).875(w).832(w).798(w).716(m).643(w).603(w).543(w).515(w).418(w). HRMS(ESI):m / zC 11 H 13 N2O[M+H] + Calculated value: 189.1028; Found: 189.1020. MS (EI): m / z (%) = 117.0 (10.08), 144.1 (17.47), 145.1 (100), 146.1 (79.0), 188.1 (53.04, [M+]).

[0475] 1-(3,5-Dimethoxyphenyl)propan-2-one (10)

[0476]

[0477] Compound 10 was synthesized according to the general procedure, purified by column chromatography (hexane / ethyl acetate 20:1), and isolated as a colorless liquid in 97% yield. The analytical data were consistent with those reported in the literature. 1H NMR (400MHz.CDCl3): δ6.37(tJ=2.23Hz.3H).6.35(dJ=2.25Hz.6H).3.78(s.5H).3.61(s.2H).2.15(s.3H). 13 CNMR(101MHz.CDCl3): δ=206.4.161.2.136.5.107.6.99.2.55.4.51.5.29.2. IR(cm -1 ):3000(w).2939(w).2838(w).2349(w).1711(m).1596(vs).1463(m).1431(m).1350(m).129 3(w).1206(s).1159(s).1068(m).927(w).836(w).704(w).529(w).487(w).459(w).421(w). MS (EI): m / z (%) = 77.0 (23.48), 91.1 (25.95), 151.1 (100), 152.1 (86.0), 194.1 (86.32, [M+]).

[0478] 1-(3-Methylbenzo[b]thiophen-5-yl)propan-2-one (11)

[0479]

[0480] Compound 1 was synthesized according to the general procedure, purified by column chromatography (hexane / ethyl acetate 20:1), and isolated as a colorless liquid in 97% yield. 1 H NMR(400MHz.CDCl3): δ7.81(dJ=8.20Hz.1H).7.67–7.38(m.1H).7.19(dd.J=8.29.1 .69Hz.1H).7.09(dJ=1.41Hz.1H).3.84(s.2H).2.43(dJ=1.24Hz.3H).2.18(s.3H). 13 CNMR(101MHz.CDCl3): δ206.8.140.3.139.2.132.1.130.1.125.7.123.2.122.6.122.4.51.2.29.4.14.0. IR(cm -1):3076(w).2914(w).2855(w).1709(vs).1599(w).1558(w).1442(w).1355(w).1318(w).1227(w).1157(w).1 090(w).1049(w).1020(w).985(w).883(w).834(w).777(w).736(w).626(w).579(w).546(w).521(w).402(w). HRMS(ESI):m / z C 12 H 13 OS[M+H] + Calculated value: 205.0687; experimental value: 205.0679.

[0481] MS (EI): m / z (%) = 115.0 (14.3), 128.0 (9.61), 161.1 (100), 162.0 (16.09), 204.0 (30,0 [M+]).

[0482] 1-(Benzo[d][1.3]dioxol-5-yl)propan-2-one (12)

[0483]

[0484] Compound 12 was synthesized according to the general procedure, purified by column chromatography (hexane / ethyl acetate 20:1), and isolated as a colorless liquid in 76% yield. The analytical data were consistent with those reported in the literature. 1 H NMR (400MHz.CDCl3): δ=6.7(dJ=7.82Hz.1H).6.7(dJ=1.73Hz.1H).6.6(dd.J=7.91.1.73Hz.1H).5.9(s.2H).3.6(s.2H).2.1(s.3H). 13 CNMR(101MHz.CDCl3): δ=206.6.147.9.146.7.127.9.122.6.109.8.108.5.101.1.50.5.29.1. IR(cm -1):2995(w).2894(w).2778(w).1708(s).1608(w).1488(vs).1443(s).1355(m).1246(vs).11 87(w).1159(m).1100(w).1038(s).925(m).813(w).649(w).603(w).509(w).465(w).432(w). MS (EI): m / z (%) = 51.0 (10.68), 77.0 (20.48), 105.0 (6.36), 135.0 (100), 136.0 (10.03), 178.0 (27.13, [M+]).

[0485] 2-Methyl-1H-indole (13)

[0486]

[0487] Compound 13 was synthesized according to the general procedure, purified by column chromatography (hexane / ethyl acetate 20:1), and isolated as a colorless liquid in 71% yield. The analytical data were consistent with those reported in the literature. 1 H NMR (400MHz.CDCl3): δ=7.6–7.3(m.1H).7.2(dd.J=14.67.7.20Hz.1H).7.1–6.8(m.2H).6.1(s.1H).2.4(s.3H). IR(cm -1 ):3377(m).3052(w).2939(w).1880(w).1800(w).1766(w).1618(w).1580(w).1547(w).1454(w).1401(w).1344(w).128 4(w).1216(w).1151(w).1112(w).1036(w).1008(w).978(w).925(w).781(vs).731(m).629(s).505(s).434(m).408(m). MS (EI): m / z (%) = 64.9 (6.4), 77.0 (11.8), 103.0 (9.21), 130.0 (100), 131.0 (70.17), 132.0 (6.54, [M+]).

[0488] (4-Chlorophenyl)trimethylsilane (14)

[0489]

[0490] Compound 14 was synthesized according to the general procedure, purified by column chromatography (hexane / ethyl acetate 20:1), and isolated as a colorless liquid in 92% yield. 1 H NMR (400MHz.CDCl3): δ=7.50(dJ=7.82Hz.2H).7.20(dJ=7.64Hz.2H).3.70(s.2H).2.17(s.3H).0.27(s.9H). 13 C NMR (101MHz.CDCl3): δ=206.4.139.1.134.8.133.9.128.9.51.1.29.4.-1.0. 29 Si NMR (80MHz. CDCl3): δ=-4.05. IR(cm -1 ):3067(w).3013(w).2954(w).2896(w).1712(s).1600(w).1554(w).1500(w).1395(w).1356(w).124 7(m).1157(w).1106(m).838(vs).754(m).721(w).693(w).666(w).622(w).560(m).500(w).400(w). IR(cm -1 ):73.0(13.38),135.0(19.29),148.1(25.03),163.1(10.03),191.1(100),192.1(20.89),206.1(51.11,[M+]).

[0491] 1-(4-Benzoylphenyl)propan-2-one (15)

[0492]

[0493] Compound 15 was synthesized according to the general procedure, purified by column chromatography (hexane / ethyl acetate 20:1), and isolated as a colorless liquid in 71% yield. The analytical data were consistent with those reported in the literature. 1 H NMR (400MHz.CDCl3): δ=7.82–7.77(m.3H).7.75(dJ=8.23Hz.1H).7.62–7.55(m.1H).7.48(td.J=7 .43.3.56Hz.2H).7.31(dd.J=8.14.3.87Hz.1H).7.23(dJ=8.24Hz.1H).2.63(s.2H).2.17(s.3H). 13C NMR (101MHz.CDCl3): δ=211.0.198.7.139.0.138.2.137.8.132.5.130.7.130.2.130.0.129.6.128.4.53.9.29.4. IR(cm -1 ):2931(w).1700(vs).1657(vs).1605(m).1447(m).1415(m).1362(m).1317(m).1278(s).11 78(m).1148(m).1020(w).925(m).745(w).705(m).534(m).510(m).465(m).433(s).406(m). MS (EI): m / z (%) = 77.0 (23.38), 90.0 (20.42), 105.0 (28.96), 118.0 (24.95), 196.1 (100; 197.1 (15.24, [M+]).

[0494] 1-(4-Vinylphenyl)propan-2-one(16)

[0495]

[0496] Compound 16 was synthesized according to the general procedure, purified by column chromatography (hexane / ethyl acetate 20:1), and isolated as a colorless liquid in 90% yield. The analytical data were consistent with those reported in the literature. 1 H NMR(400MHz.CDCl3): δ=7.38(dJ=8.2Hz.1H).7.17(dJ=8.1Hz.1H).6.70(dd.J=17.6. 10.9Hz.1H).5.74(dJ=17.6Hz.1H).5.24(dJ=10.9Hz.1H).3.68(s.1H).2.15(s.1H). 13 C NMR (101MHz.CDCl3): δ=206.3.136.5.133.9.129.7.114.0.50.8.29.4. IR(cm -1):3086(w).3005(w).2918(w).2350(w).2304(w).2128(w).1910(w).1822(w).1710(vs).1630(w).1510(w).1407(w).1 356(w).1228(w).1158(w).1114(w).991(w).909(w).845(w).802(w).721(w).647(w).601(w).539(w).477(w).413(w). MS (EI): m / z (%) = 91.0 (18.59), 115.1 (36.12), 117.1 (100), 118.1 (24.45), 160.1 (31.47, [M+]).

[0497] 1-(4-(Dimethylamino)phenyl)propan-2-one (17)

[0498]

[0499] Compound 17 was synthesized according to the general procedure, purified by column chromatography (hexane / ethyl acetate 20:1), and isolated as a colorless liquid in 90% yield. The analytical data were consistent with those reported in the literature. 1 H NMR (400MHz.CDCl3): δ=7.07(dJ=8.57Hz.2H).6.72(dJ=8.30Hz.2H).3.58(s.2H).2.94(s.6H).2.12(s.3H). 13 CNMR(101MHz.CDCl3)δ203.3.132.7.111.0.69.8.54.9.40.0.29.4.26.8. IR(cm -1 ):969(w).2913(w).2805(w).1705(m).1588(vs).1519(s).1353(m).1229(m).1151(vs).945( m).901(w).823(m).762(w).698(w).593(w).563(m).533(m).510(m).484(w).432(w).400(w). MS (EI): m / z (%) = 91.0 (6.2), 118.0 (14.88), 133.1 (4.12), 134.1 (100), 135.1 (10.75), 177.1 (12.1, [M+]).

[0500] Preparation of metal complexes

[0501] L1-Pd(dba):

[0502]

[0503] 32.8 mg (0.058 mmol) of L1 and 39.2 mg (0.058 mmol of Pd, 15.6 % Pd) were suspended in 0.5 ml of THF in a J. Young NMR tube. A dark red solution formed and was shaken for 1 hour. Single crystals of L1-Pd(dba) were obtained by diffusing pentane into the concentrated THF solution.

[0504] 31 P NMR (162MHz, THF): δ = 67.1 (d, 2 J PP =120.4Hz,P + Pip3),20.0(d, 2 J PP =121.3Hz,PCy2).

[0505] L2-Pd(dba):

[0506]

[0507] 25 mg (0.049 mmol) of L2 and 33.5 mg (0.049 mmol of Pd, 15.6 % Pd) were suspended in 0.5 ml of THF in a J. Young NMR tube. A dark red solution formed and was shaken for 1 hour. 0.5 equivalents of dba were used to obtain L2-Pd(dba) as an orange solid.

[0508] 1 H NMR (400MHz, THF): δ = 7.74 (d, J = 15.98Hz, 3H), 7.70–7.65 (m, 5H), 7.40–7.35 (m, 9H), 7.22 (d, J = 16.01Hz, 4H) ), 3.06(d,J=12.91Hz,12H),1.88–1.69(m,11),1.69–1.59(m,8H),1.54–1.39(m,12H),1.39–0.99(m,11H). 31 P NMR (162MHz, THF): δ = 75.6 (d, 2 J PP =120.8Hz,P + Pip3),22.2(d, 2 J PP =121.2Hz,PCy2).

[0509] L1-Pd(oTol)Br:

[0510]

[0511] 32.8 mg (0.058 mmol) of L1 and 39.2 mg (0.058 mmol Pd, 15.6 % Pd) were suspended in 0.5 ml of THF in a J. Young NMR tube. A dark red solution formed and was shaken for 1 hour. Then, 0.1 ml (0.863 mmol, 15 equivalents) of 4-bromotoluene was added, and the mixture was shaken overnight. By diffusing pentane into the concentrated THF solution, a single crystal of L1-Pd(oTol)Br was obtained.

[0512] 31 P NMR (162MHz, THF): δ = 71.4 (d, 2 J PP =103.8Hz,P + Pip3),12.5(d, 2 J PP =103.2Hz,PCy2).

[0513] L3-Pd(oTol)Br:

[0514]

[0515] 30.0 mg (0.032 mmol) of L3 and 41.8 mg (0.062 mmol Pd, 15.6 % Pd) were suspended in 0.5 ml of THF in a J. Young NMR tube. A dark red solution formed and was shaken for 1 hour. Then, 0.15 ml (1.23 mmol, 20 equivalents) of 4-bromotoluene was added, and the mixture was shaken overnight. By diffusing pentane into the concentrated THF solution, a single crystal of L3-Pd(oTol)Br was obtained.

[0516] 31 P NMR (162MHz, THF): δ = 72.6 (d, 2 J PP =64.4Hz,P + Pip3),25.6(d, 2 J PP =64.4Hz,PCy2).

[0517] L3-Pd(oTol)Cl:

[0518]

[0519] 30.0 mg (0.032 mmol) of L3 and 41.8 mg (0.062 mmol Pd, 15.6 % Pd) were suspended in 0.5 ml of THF in a J. Young NMR tube. A dark red solution formed and was shaken for 1 hour. Then, 0.15 ml (1.23 mmol, 20 equivalents) of 4-chlorotoluene was added, and the mixture was shaken overnight. By diffusing pentane into the concentrated THF solution, a single crystal of L3-Pd(oTol)Cl was obtained.

[0520] 31 P NMR (162MHz, THF): δ = 72.6 (d, 2 J PP =64.4Hz,P + Pip3),25.6(d, 2 J PP =64.4Hz,PCy2). Isomers: 71.4(d, 2 J PP =86.7Hz,P + Pip3),25.0(d, 2 J PP =87.2Hz,PCy2).

[0521] L2-PdCl2:

[0522]

[0523] 25.0 mg (0.049 mmol) of L2 and 12.8 mg (0.049 mmol, 1 equivalent) of Pd(MeCN)2Cl2 were suspended in 0.5 ml of THF in a J. Young NMR tube. A red solution quickly formed and was shaken for 1 hour, during which time L2-PdCl2 precipitated as an orange solid.

[0524] 31 P NMR (162MHz, THF): δ = 51.4 (d, 2 J PP =15.3Hz,P + Pip3),44.7(d, 2 J PP =15.1Hz,PCy2).

[0525] L3-PdCl2:

[0526]

[0527] 20.0 mg (0.041 mmol) of L3 and 10.7 mg (0.041 mmol, 1 equivalent) of Pd(MeCN)2Cl2 were suspended in 0.5 ml of THF in a J. Young NMR tube. A red solution quickly formed and was shaken for 1 hour, during which time L2-PdCl2 precipitated as an orange solid.

[0528] 31 P NMR (162MHz, THF): δ = 85.3 (d, 2 J PP =58.0Hz,P + Pip3),47.5(d, 2 J PP =58.0Hz,PCy2).

[0529] L7-PdCl2:

[0530]

[0531] 25.0 mg (0.043 mmol) of L7 and 11.1 mg (0.043 mmol, 1 equivalent) of Pd(MeCN)2Cl2 were suspended in 0.5 ml of THF in a J. Young NMR tube. A red solution quickly formed and was shaken for 1 hour, during which time L7-PdCl2 precipitated as an orange solid.

[0532] 31 P NMR (162MHz, THF): δ = 85.3 (d, 2 J PP =58.1Hz,P + ),47.5(d, 2 J PP =58.0Hz,PCy2).

[0533] L1-AuCl:

[0534]

[0535] 93.3mg (0.164mmol) L1 and 50.0mg Au (tht) Cl (0.164mmol) were suspended in 4ml pentane and stirred overnight. A colorless suspension was formed, and the solid was filtered out, washed with 3 × 3ml pentane, and dried in a vacuum. L1-AuCl (110mg, 0.137mmol) was obtained as a colorless solid in an 88% yield.

[0536] 1 H NMR (400MHz, C6D6): δ = 7.29–7.23 (m, 2H, Ph邻位 ),7.22–7.17(m,2H,Ph 间位 ),7.11–7.05(m,1H,Ph 对位 ),3.02(q, 3 J HP =5.0Hz,12H,Pip position 1CH2),2.56–2.46(m,2H,Cy position 3,CH2),1.98–1.76(m,4H,Cy position 1,CH+Cy position 2,CH2),1.66–1.52(m,4H,Cy position 2+position 4,CH2),1.50–1.32(m,24H,Pip position 2+position 3CH2;Cy position 3,CH2),1.29–1.18(m,2H,Cy position 4,CH2),1.17–1.05(m,4H,Cy position 2,CH2). 13 C NMR (101MHz, C6D6): δ = 141.3 (dd, 2 J CP =8.6,2.6Hz,Ph 本位 ,C),136.7(dd, 3 J CP =6.0,2.4Hz,Ph 邻位 ,CH),127.9(s,Ph 间位 ,CH),125.6(d, 2 J=2.5Hz,CH),48.2(s,Pip position 1,CH),41.0(dd, 1 J CP =37.9Hz, 3 J CP =3.3Hz,Cy position 1,CH),33.3(d, 3 J CP =2.4Hz,Cy position 3,CH2),31.0(s,Cy position 3,CH2),29.7(dd, 1 J CP =196.7,60.4Hz,P–C - –P),28.2(d, 2 J CP =13.6Hz,Cy position 2,CH2),27.3(d, 2 J CP =12.1Hz,CH2),26.5(s,Cy position 4,CH2),26.4(d, 2 J CP =5.0Hz,Pip position 2,CH2),25.0(s,Pip position 3,CH2). 31PNMR (162MHz, C6D6): δ = 54.2 (d, 2 J PP =74.8Hz,P + Pip3),31.0(d, 2 J PP =75.3Hz,PCy2).

[0537] L2-AuCl:

[0538]

[0539] 83.2mg (0.164mmol) L1 and 50.0mg Au (tht) Cl (0.164mmol) were suspended in 4ml pentane and stirred overnight. A colorless suspension was formed, and the solid was filtered out, washed with 3 × 3ml pentane, and dried in a vacuum. L2-AuCl (99mg, 0.134mmol) was obtained as a colorless solid in an 86% yield.

[0540] 1 H NMR (400MHz, C6D6): δ = 3.09 (q, 3 J HP =5.4 Hz, 12H, Pip position 1, CH2), 2.06–1.91 (m, 6H, Cy position 1, CH, + Cy position 3, CH2), 1.83–1.70 (m, 4H, Cy position 2 + position 3, CH2), 1.68–1.57 (m, 6H, Cy position 3 + position 4, CH2), 1.54 (dd, 3 J HP =14.4,9.9 Hz,3H,CH3),1.50–1.42 (m,6H,Pip position 3,CH2),1.39–1.29 (m,12H,Pip position 2,CH2),1.27–1.07 (m,6H,Cy position 2+position 3,CH2). 13 CNMR (101MHz, C6D6): δ=48.0(s, Pip position 1, CH2, 37.8(dd, 1 J CP =39.2Hz, 3 J CP =4.3Hz,Cy position 1,CH),31.7(d, 3 J CP =3.9Hz,Cy position 3,CH2),30.9(s,Cy position 3,CH2),27.7(d, 2 J CP =11.7Hz,Cy position 2,CH2),27.3(d,2 J CP =14.0Hz,Cy position 2,CH2),26.7(s,Pip position 2,CH2),26.7(s,Cy position 4,CH2),25.0(s,Pip position 3,CH2),16.4(dd, 3 J CP =6.1,1.8Hz,CH3),7.2(dd, 1 J CP =196.9,71.0Hz,P–C - –P). 31 P NMR (162MHz, C6D6): δ = 62.4 (d, 2 J PP =83.0Hz,P + Pip3),35.9(d, 2 J PP =83.1Hz,PCy2).

[0541] L5-AuCl:

[0542]

[0543] 87.8 mg (0.164 mmol) of L1 and 50.0 mg of Au (tht) Cl (0.164 mmol) were suspended in 4 ml of pentane and stirred overnight. A colorless suspension was formed, and the solid was filtered out, washed with 3 × 3 ml of pentane, and dried in a vacuum. L5-AuCl (65 mg, 0.085 mmol) was obtained as a colorless solid in a yield of 54%.

[0544] 1 H NMR (400MHz, C6D6): δ = 3.05 (q, 3 J = 5.3 Hz, 12H, Pip position 1, CH2), 2.52–2.33 (m, 3H, iPr, CH, Cy position 3, CH2), 2.11–1.98 (m, 4H, Cy position 1, CH, Cy position 3, CH2), 1.85–1.69 (m, 4H, Cy position 2, CH2), 1.66–1.54 (m, 4H, Cy position 2+position 3, CH2), 1.51–1.31 (m, 20H, Pip position 2+position 3+Cy position 3, CH2), 1.29–1.08 (m, 12H, iPr CH3, Cy position 2+position 4, CH2). 13 C NMR (101 MHz, C6D6): δ = 48.6 (s, Pip position 1, CH2), 41.8 (d, 1 J CP=35.6Hz,Cy position 1,CH),34.7(s,Cy position 3,CH2),32.6(s,Cy position 3,CH2,30.5(d, 2 J CP =11.4Hz,iPr CH(CH3)2,28.3(d, 2 J CP =13.7Hz,Cy position 2,CH2),27.9(d, 2 J CP =12.2Hz,Cy position 2,CH2),26.8(d, 3 J CP =4.8Hz,iPr,CH(CH3)2),26.6(d, 3 J=1.6Hz,Cy position 4,CH2),26.5(d, 3 J CP =4.6Hz,Pip position 2,CH2),25.1(s,Pip position 3). 31 PNMR (162MHz, C6D6): δ = 61.5 (d, 2 J PP =82.1Hz,P + Pip3),39.3–38.5(d br, 2 J PP =82.1Hz,PCy2).

[0545] L6-AuCl:

[0546]

[0547] 74.6mg (0.164mmol) L1 and 50.0mg Au (tht) Cl (0.164mmol) were suspended in 4ml pentane and stirred overnight. A colorless suspension was formed, and the solid was filtered out, washed with 3 × 3ml pentane, and dried in a vacuum. L6-AuCl (87mg, 0.085mmol) was obtained as a colorless solid in an 81% yield.

[0548] 1 H NMR (400MHz, C6D6): δ = 3.11 (q, 3 J=5.8Hz,12H,Pip position 1,CH2),1.60(dd, 3 J HP =14.8,9.5Hz,3H CH3),1.51(m,6H,Pip position 3CH2),1.35(d, 3 J HP =14.1Hz,18H,t Bu, CH3), 1.31–1.23 (m, 12H, Pip position 2CH2). 13 C NMR (101 MHz, C6D6): δ = 47.8 (s, Pip position 1, CH2), 40.9 (dd, 1 J CP =31.7Hz, 3 J CP =5.7Hz, t Bu C(CH3)3),31.9(d, 2 J CP =5.9Hz, t Bu C(CH3)3),26.9(d, 3 J CP =4.4Hz,Pip position 2,CH2),24.9(s,Pip position 3,CH2),18.4(dd, 2 J CP =4.9,2.0Hz,CH3),12.4(dd, 1 J CP =197.3,70.8Hz,P–C - –P). 31 P NMR (162MHz, C6D6): δ = 60.7 (d, 2 J PP =87.1Hz,P + Pip3),58.3(d, 2 J PP =87.1Hz,PCy2).

[0549] L3-AuCl:

[0550]

[0551] 79.7mg (0.164mmol) L3 and 50.0mg Au (tht) Cl (0.164mmol) are suspended in 4ml pentane and stirred overnight. A colorless suspension is formed, and the solid is filtered out, washed with 3 × 3ml pentane, and dried in a vacuum. L3-AuCl (80mg, 0.111mmol) is obtained as a colorless solid in a yield of 71%.

[0552] 1 H NMR (400MHz, C6D6): δ = 7.21–7.16 (m, 2H, Ph 邻位 ,CH2),7.13–7.06(m,2H,Ph 间位 ,CH2),7.05–6.98(m,1H,Ph对位 ,CH2),3.85(s,2H,N(CH2)2N),2.68(dq, 3 J=8.6,5.3Hz,2H,N(CH2)2N),2.42(d, 3 J HP =9.2Hz,6H,NCH3),2.01(s,3H,PCy position 1,CH+PCy2 position 3,CH2),1.91–1.80(m,2H,PCy2 position 1,CH),1.74(d, 3 J = 12.7 Hz, 2H, PCy2 position 3, CH2), 1.69–1.61 (m, 4H, PCy position 2 + PCy2 position 2, CH2), 1.59–1.48 (m, 4H, PCy position 4 + PCy2 position 3, CH2), 1.46–1.33 (m, 3H, PCy2 position 4 + position 2, CH2), 1.32–1.18 (m, 4H, PCy2 position 2, CH2), 1.15–1.00 (m, 7H, PCy2 position 2 + position 3, CH2), 0.84–0.55 (m, 4H, PCy2 position 2 + position 4, CH2). 13 C NMR (101MHz, C6D6): δ = 140.5 (dd, 2 J CP =14.0,2.9Hz,Ph 本位 ,C),136.2(s,Ph 邻位 ,CH),127.8(s,Ph 间位 ,CH),125.6(s,Ph 对位 ,CH),47.3(d, 2 J=6.8Hz,N(CH2)2N),39.2(dd, 1 J PCP =85.1Hz, 3 J CP =5.4Hz,PCy position 1,CH),37.5(d, 1 J CP =38.7Hz,PCy2,CH),32.9(d, 2 J CP =7.0Hz,N(CH3)),30.4(d, 3 J CP =2.4Hz,PCy2 position 3,CH2),29.9(s,PCy2 position 3,CH2),28.2(dd, 1 J CP =114.4,90.4Hz,P–C - –P),27.2(d,2 J CP =12.1Hz,PCy position 2,CH2),26.8(d, 2 J CP =13.6Hz,PCy2 position 2,CH2),26.5(d, 2 J CP =13.6Hz,PCy2 position 3,CH2),26.2(s,PCy position 3,CH2),25.9(s,PCy2 position 4,CH2),22.4(s,PCy position 4,CH2). 31 P NMR (162MHz, C6D6): δ = 61.3 (d, 2 J PP =53.1Hz,P + ),26.3(d, 2 J PP =52.5Hz,PCy2).

[0553] L10-AuCl:

[0554]

[0555] The synthesis of L10AuCl was carried out according to the general procedure. Colorless crystals suitable for single crystal X-ray diffraction experiments were obtained from the washing solution. Yield: (87.0 mg, 0.119 mmol, 76%).

[0556] 1 H NMR (400MHz, CD2Cl2): δ = 7.30 (d, 3 J HH =7.2Hz,1H,oTol 邻位 ),7.20(d, 3 J HH =7.3Hz,1H,oTol 间位 ),7.15–7.02(m,2H,oTol 间位'+对位 ),3.69–3.49(m,2H,NC2H4N),3.14–3.02(m,2H,NC2H4N),2.77(dd, 3 J HP =28.2Hz, 5 J CP=9.1Hz,6H,NCH3),2.58(s,3H,CH3,oTol),2.28(s,1H,Cy,H2),2.00–1.55(m,14H,Cy+PCy2,H1-4),1.53–1.37(m,5H,Cy+PCy2,H2-4),1.34–0.90(m,14H,Cy+PCy2,H2-4),0.71–0.56(m,1H,PCy2,H3)ppm。 13 C{ 1 H}NMR(101MHz,CD2Cl2):δ=141.8(dd, 2 J CP =5.6,3.3Hz,oTol 本位 ),139.4(dd, 3 J CP =4.9,2.2Hz,oTol 邻位 ),139.1(dd, 3 J CP =12.9,3.0Hz,oTol 邻位' ),131.4(t, 4 J CP =2.0Hz,oTol 间位 ),126.9(t, 4 J CP =2.4Hz,oTol 间位' ),125.9(t, 5 J CP =2.2Hz,oTol 对位 ),48.3–48.0(m,NC2H4N),41.5(dd, 1 J CP =85.7Hz, 3 J CP =5.8Hz,Cy,C1),40.4(dd, 1 J CP =38.7Hz, 3 J CP =5.2Hz,PCy2,C1),37.24(dd, 1 J CP =37.4Hz, 3 J CP =1.6Hz,PCy2,C1),34.6(d, 2 J CP =7.0Hz;NCH3),34.0(d, 2 J CP =6.6Hz,NCH3),32.4(d, 2 JCP =2.6Hz,Cy,C2),31.7(s,Cy,C2),30.8(d, 3 J CP =1.8Hz,Cy,C3),28.7(d, 3 J CP =4.2Hz,PCy2,C3),27.9(dd, 2 J CP =12.9Hz, 4 J CP =9.5Hz,PCy2,C2),27.5(dd, 2 J CP =13.1Hz, 2 J CP =4.8Hz,PCy2,C2),27.3–27.1(m,PCy2,C3),26.8–26.7(m,PCy2,C4),26.5(d, 4 J CP =1.6 Hz, Cy, C4), 22.6 (s, CH3, oTol) ppm. No PCP signal was observed. 31 P{ 1 H}NMR (162MHz, CD2Cl2): δ = 59.2 (d, 2 J PP =54.1Hz,PCy(MeNC2H4NMe)),31.0(d, 2 J PP =54.1Hz,PCy2)ppm. IR(ATR):2919(m)2848(m),1444(m),1219((m),1176(m),1020(s),950(s),922(m),729(m),548(m),484(m)cm -1 . Melting point: 192℃ (decomposition). 30 H 50 Elemental analysis of AuClN2P2: Calculated: C 49.15; H 6.87; N 3.82, Found: C 48.80; H 6.87; N 3.78.

[0557] L11-AuCl:

[0558]

[0559] The synthesis of L11AuCl was carried out according to the general procedure. Colorless crystals suitable for single crystal X-ray diffraction experiments were obtained by slow vapor diffusion of pentane into a saturated DCM solution of the compound. Yield: (94.0 mg, 0.119 mmol, 76%).<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0560] <h2 style=";text-align:left;direction:ltr"> 1 <h2 style=";text-align:left;direction:ltr"> H NMR(400MHz,CD2Cl2):δ=7.33(d,<h2 style=";text-align:left;direction:ltr"> 3 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> HH <h2 style=";text-align:left;direction:ltr"> <7.5Hz,1H,oTol<h2 style=";text-align:left;direction:ltr"> 邻位 <h2 style=";text-align:left;direction:ltr"> ),7.20(d,<h2 style=";text-align:left;direction:ltr"> 3 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> HH <h2 style=";text-align:left;direction:ltr"> =7.4Hz,1H,oTol<h2 style=";text-align:left;direction:ltr"> 间位 <h2 style=";text-align:left;direction:ltr"> ),7.15–7.01(m,2H,oTol<h2 style=";text-align:left;direction:ltr"> 间位'+对位 <h2 style=";text-align:left;direction:ltr"> ),4.13–4.02(m,1H,NCH(CH3)2),3.94–3.84(m,1H,NCH(CH3)2'),3.65–3.54(m,2H,NC2H4N),3.07–2.97(m,2H,NC2H4N'),2.52(s,3H,CH3,oTol),2.45–2.27(m,2H,Cy,H2),1.90–0.65(m,43H,Cy / PCy2,CH3)ppm.<h2 style=";text-align:left;direction:ltr"> 13 <h2 style=";text-align:left;direction:ltr"> C{<h2 style=";text-align:left;direction:ltr"> 1 <h2 style=";text-align:left;direction:ltr"> H}NMR(101MHz,CD2Cl2):δ=142.5(dd,<h2 style=";text-align:left;direction:ltr"> 2 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> CP <h2 style=";text-align:left;direction:ltr"> =7.1,3.1 Hz,oTol<h2 style=";text-align:left;direction:ltr"> 本位 <h2 style=";text-align:left;direction:ltr"> ),139.4–139.3 (m,oTol<h2 style=";text-align:left;direction:ltr"> 邻位 <h2 style=";text-align:left;direction:ltr"> ),139.2(d,<h2 style=";text-align:left;direction:ltr"> 3 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> CP <h2 style=";text-align:left;direction:ltr"> <3.2Hz, oTol<h2 style=";text-align:left;direction:ltr"> 邻位' <h2 style=";text-align:left;direction:ltr"> ),131.5(t,<h2 style=";text-align:left;direction:ltr"> 4 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> CP <h2 style=";text-align:left;direction:ltr"> <1.8Hz, oTol<h2 style=";text-align:left;direction:ltr"> 间位 <h2 style=";text-align:left;direction:ltr"> ),126.9(t,<h2 style=";text-align:left;direction:ltr"> 4 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> CP <h2 style=";text-align:left;direction:ltr"> <2.3Hz, oTol<h2 style=";text-align:left;direction:ltr"> 间位' <h2 style=";text-align:left;direction:ltr"> ),126.0(t,<h2 style=";text-align:left;direction:ltr"> 5 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> CP <h2 style=";text-align:left;direction:ltr"> <2.2Hz, oTol<h2 style=";text-align:left;direction:ltr"> 对位 <h2 style=";text-align:left;direction:ltr"> ),44.2(dd,<h2 style=";text-align:left;direction:ltr"> 2 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> CP <h2 style=";text-align:left;direction:ltr"> <24.9Hz,<h2 style=";text-align:left;direction:ltr"> 2 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> CP <h2 style=";text-align:left;direction:ltr"> <8.4Hz,NCH(CH3)2),43.1(dd,<h2 style=";text-align:left;direction:ltr"> 1 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> CP <h2 style=";text-align:left;direction:ltr"> <82.6Hz,<h2 style=";text-align:left;direction:ltr"> 3 <h2 style=";text-align:left;direction:ltr"> J<h2 style=";text-align:left;direction:ltr"> CP <h2 style=";text-align:left;direction:ltr"> =5.9Hz,Cy,C1),41.1–40.4(m,PCy2,C1),37.5(dd,<h2 style=";text-align:left;direction:ltr"> 2J CP = 19.1 Hz, 4 J CP = 8.0 Hz, NC2H4N), 34.6 (dd, 2 J CP = 73.1 Hz, 4 J CP = 3.8 Hz, Cy, C2), 30.7 (s, Cy / PCy2), 29.8 (d, J CP = 1.9 Hz, Cy / PCy2), 28.2 (d, J CP = 12.4 Hz, Cy / PCy2), 28.1 (d, J CP = 8.9 Hz, Cy / PCy2), 27.9 (d, J CP = 6.1 Hz, Cy / PCy2), 27.7 (Cy / PCy2), 27.6 (d, J CP = 14.3 Hz, Cy / PCy2), 27.4–27.3 (m, Cy / PCy], 27.2 (Cy / PCy2), 26.8 (dd, J CP = 4.6, 1.7 Hz, Cy / PCy2), 26.7 (d, J CP = 1.6 Hz), 26.6 (d, J CP = 3.9 Hz), 23.2 (dd, 3 J CP = 4.3, 1.6 Hz, CH3, iPr + iPr'), 22.4 (s, CH3, oTol), 21.6 (d, 3 J CP = 1.8 Hz, CH3, iPr), 21.4 (d, 3 J CP = 2.3 Hz, CH3, iPr') ppm. No PCP signal was observed. 31 P{ 1 H} NMR (162 MHz, CD2Cl2): δ = 58.9 (d, 2 J PP ?= 57.0 Hz, PCy (iPrNC2H4NiPr)), 29.8 (d, 2 J PP = 57.0 Hz, PCy2) ppm. IR (ATR): 2925 (m), 2848 (m), 1444 (w), 1175 (s), 1102 (m), 1065 (s), 1018 (s), 994 (m), 970 (m), 917 (m), 886 (m), 728 (m), 548 (m), 529 (m), 473 (s), 441 (m) cm -1. Melting point: 250℃ (decomposition). 34 H 58 Elemental analysis of AuClN2P2: Calculated values: C 51.74; H 7.41; N 3.55, Found values: C 52.08; H 7.58; N 3.55.

[0561] L12-AuCl:

[0562]

[0563] The synthesis of L12AuCl was carried out according to the general procedure. Colorless crystals suitable for single crystal X-ray diffraction experiments were obtained by slow vapor diffusion of pentane into a saturated DCM solution of the compound. Yield: (92.0 mg, 0.109 mmol, 70%).

[0564] 1 H NMR (400MHz, CD2Cl2): δ = 7.28 (d, 3 J HH =7.5Hz,1H,oTol 邻位 ),7.21(d, 3 J HH =7.3Hz,1H,oTol 间位 ),7.13–7.03(m,2H,oTol 间位'+对位 ),3.66–3.53(m,2H,NC2H4N),3.33–3.16(m,2H,NCH2),3.16–2.98(m,4H,NCH2+NC2H4N),2.56(s,3H,CH3 ,oTol),2.44–2.33(m,1H,Cy / PCy2),2.26–2.16(m,1H,Cy / PCy2),1.96–1.03(m,34H,Cy / PCy2),0.96(dd, 3 J HH =6.6,4.2Hz,12H,CH3,iPen),0.92–0.59(m,3H,Cy / PCy2)ppm. 13 C{ 1 H}NMR (101MHz, CD2Cl2): δ = 142.0 (dd, 2 J CP =5.8,3.2Hz,oTol 本位 ),139.2(d, 3 J CP =3.0Hz,oTol 邻位 ),139.1(d, 3 J CP =3.0Hz,oTol邻位' ),131.5(d, 4 J CP =1.9Hz,oTol 间位 ),126.9(d, 4 J CP =2.8Hz,oTol 间位' ),126.1(s,oTol 对位 ),46.4(t,J=6.1Hz,NCH2),45.5(dd, 2 J CP =18.7Hz, 4 J CP =6.8Hz,NC2H4N),41.9(dd, 1 J CP =41.9Hz, 3 J CP =5.4Hz,Cy,C1),41.3(t,J=5.5Hz,PCy2,C1),38.7–38.2(m,CH2,iPen+PCy2,C1),33.7(dd,J CP =6.4,3.1Hz,Cy / PCy2),30.6(d, 2 J CP =21.2Hz,Cy,C2),28.22–26.62(m,Cy / PCy2),23.2(d, 5 J CP =4.1Hz,CH3,iPen),22.8(d, 5 J CP =7.2 Hz, CH3,iPen), 22.4 (s, CH3,oTol) ppm. No PCP signal was observed. 31 P{ 1 H}NMR (162MHz, CD2Cl2): δ = 60.9 (d, 2 J PP =55.8Hz,PCy(iPenNC2H4NiPen)),31.3(d, 2 J PP =55.8Hz,PCy2)ppm. IR(ATR):2923(s),2848(m),1444(m),1156(s),1113(m),1067(s),1023 (s),996(m),921(m),888(w),754(m),729(s),545(m),515(m),471(s)cm -1 . Melting point: 191℃ (decomposition). 38 H 66Elemental analysis of AuClN2P2: Calculated values: C 53.99; H 7.87; N 3.31, Found values: C 53.68; H 8.11; N 3.25.

[0565] L13-AuCl:

[0566]

[0567] The synthesis of L13AuCl was carried out according to the general procedure. Colorless crystals suitable for single crystal X-ray diffraction experiments were obtained by slow vapor diffusion of pentane into a saturated benzene solution of the compound. Yield: (89.0 mg, 0.116 mmol, 74%).

[0568] Since two different conformers exist in solution, it is not possible to evaluate 1 H NMR and 13 C{ 1 H} NMR. Complex decomposition was observed during high temperature NMR spectroscopy. 31 P{ 1 H}NMR (162MHz, CD2Cl2): δ = 81.0 (d, 2 J PP =75.6Hz,PCy(newPenNC2H4NnewPen)),78.1(d, 2 J PP =50.0Hz,PCy(new PenNC2H4N new Pen)),36.9(d, 2 J PP =75.6Hz,PCy2),34.8(d, 2 J PP =50.0Hz, PCy2). IR(ATR):2924(s),2847(m),1443(w),1181(w),1162(w),1138(w),1108(w),1065(s),1034(m) ,1034(m),985(w),926(s),883(m),850(w),736(m),604(w),570(s),520(m),502(m),426(m)cm -1 . Melting point: 210℃ (decomposition). 32 H 62 Elemental analysis of AuClN2P2: Calculated values: C 49.97; H 8.12; N 3.64, Found values: C 49.77; H 8.14; N 3.55.

[0569] L14-AuCl:

[0570]

[0571] The synthesis of L14AuCl was carried out according to the general procedure. Colorless crystals suitable for single crystal X-ray diffraction experiments were obtained by slow vapor diffusion of pentane into a saturated DCM solution of the compound. Yield: (76.0 mg, 0.097 mmol, 62%).

[0572] 1 H NMR (400MHz, CD2Cl2): δ = 6.86 (d, 5 J HP =2.5Hz,4H,Mes 间位 ),4.29–4.16(m,1H,Cy,H1),3.7(s,2H,NC2H4N),3.6(s,2H,NC2H4N'),2.50(d, 5 J HP =3.9Hz,12H,CH3,Mes 邻位 ),2.22(s,8H,CH3,Mes 对位 +Cy,H2),2.08–1.93(m,2H,CH(CH3)2),1.79–1.58(m,4H,Cy,H3+4),1.43(dd, 3 J HP =14.8,10.6Hz,3H,PCPCH3),1.37–1.13(m,4H,Cy,H2+3),1.07(dd, 3 J HP =16.9, 3 J HH =7.0Hz,6H,CH3,iPr),0.75(dd, 3 J HP =16.9, 3 J HH =7.1Hz,6H,CH3,iPr')ppm. 13 C{ 1 H}NMR (101MHz, CD2Cl2): δ = 139.2 (d, 2 J CP =5.0Hz,Mes 本位 ),137.3(s,Mes ortho ),137.0(s,Mes 邻位' ),136.2(d, 5 J CP =1.3Hz,Mes 对位 ),131.2(s,Mes 间位 ),131.0(s,Mes 间位'),51.0(d, 2 J CP =8.8Hz,NC2H4N),40.8(dd, 1 J CP =85.4Hz, 3 J CP =2.3Hz,Cy,C1),29.4(s,Cy,C2+CH(CH3)2),26.8(d, 4 J CP =1.9Hz,Cy,C4),26.4(d, 3 J CP =14.7Hz,Cy,C3),21.6(s,CH3,Mes 邻位 ),20.9–20.8(m,CH3,iPr),20.8(s,CH3,Mes 对位 ),17.6(dd, 1 J CP =141.8,64.3Hz,PCP),15.7(d, 2 J CP =1.7Hz,PCPCH3)ppm. 31 P{ 1 H}NMR (162MHz, CD2Cl2): δ = 58.1 (d, 2 J PP =74.1Hz,PiPr2),47.9(d, 2 J PP =74.1Hz,PCy(MesNC2H4NMes)). IR(ATR):2925(w),1475(m),1245(s),1187(w),1149(m),1060(s),914(s),851( m),823(s),739(m),654(m),625(m),601(m),562(s),510(m),444(w),416(w)cm -1 . Melting point: 237℃ (decomposition). 34 H 54 Elemental analysis of AuClN2P2: Calculated: C 52.01; H 6.93; N 3.57, Found: C 51.71; H 7.02; N 3.32.

[0573] L15-AuCl:

[0574]

[0575] The synthesis of L15AuCl was carried out according to the general procedure. Colorless crystals suitable for single crystal X-ray diffraction experiments were obtained by slow vapor diffusion of pentane into a saturated DCM solution of the compound. Yield: (108 mg, 0.137 mmol, 88%).

[0576] Since two different conformers exist in solution, it is not possible to evaluate 1 H NMR and 13 C{ 1 H} NMR. Complex decomposition was observed during high temperature NMR spectroscopy. 31 P{ 1 H}NMR (162MHz, CD2Cl2): δ = 60.8 (d, 2 J PP =53.2Hz),59.6(d, 2 J PP =51.2Hz),31.9(d, 2 J PP =53.2Hz,PCy2),31.2(d, 2 J PP =51.2Hz,PCy2)ppm. IR(ATR):293(m),2848(m),1442(w),1212(m),1178(m),1012(s),922(m),8 90(m),847(w),807(w),759(w),730(m),552(m),523(m),482(m),424(m)cm -1 . Melting point: 223℃ (decomposition). 34 H 56 Elemental analysis of AuClN2P2: Calculated values: C 51.88; H 7.17; N 3.56, Found values: C 51.85; H 7.12; N 3.51.

[0577] L16-AuCl:

[0578]

[0579] Phosphine L16 (96.6 mg, 0.172 mmol) and (tetrahydrothiophene) gold (I) chloride (50.0 mg, 0.156 mmol) were dissolved in toluene (5 ml) and stirred at room temperature overnight. The solution was covered with pentane (15 ml) and left overnight. A colorless solid precipitated from the solution. The solid was filtered out and washed with pentane (3 × 5 ml). After drying in a vacuum at 50 ° C, the gold complex L7AuCl was obtained as a colorless solid. By slowly vapor diffusing pentane into a saturated DCM solution of the compound, colorless crystals suitable for single crystal X-ray diffraction experiments were obtained. Yield: (85.0 mg, 0.103 mmol, 66%).

[0580] 1 H NMR (400MHz, CD2Cl2): δ=7.27–7.20(m,2H,oTol 邻位 + 对位 ),7.16(t, 3 J HH =7.4Hz,1H,oTol 间位 ),7.08(t, 3 J HH =7.4Hz,1H,oTol 间位' ),3.82(brs,8H,Mor),3.38(brs,12H Mor),2.63–2.29(m,9H,CH3,oTol+PCy2,H3+Mor),1.94–0.98(m,20H,PCy2)ppm. 13 C{ 1 H}NMR (101MHz, CD2Cl2): δ = 143.1 (dd, 2 J CP =7.1,2.6Hz,oTol 本位 ),139.3(dd, 3 J CP =4.7,2.0Hz,oTol 邻位 ),138.1(dd, 3 J CP =7.7,2.9Hz,oTol 邻位' ),131.45(t,J CP =1.7Hz,oTol 对位 ),127.4(t,J CP =2.5Hz,oTol 间位 ),125.8(q,J CP =2.5Hz,oTol 间位' ),67.2(s,Mor,C2),48.1(s,Mor,C3),41.5(dd,1 J CP =37.6Hz, 3 J CP =2.1Hz,PCy2,C1),40.9(dd, 1 J CP =37.6Hz, 3 J CP =5.7Hz,PCy2,C1),35.3(d, 3 J CP =3.3Hz,PCy2,C3),34.4(d, 3 J CP =2.7Hz,PCy2,C3),30.9(s,PCy2,C3),30.1(d, 3 J CP =1.7Hz,PCy2,C3),28.4(d, 2 J CP =14.0Hz,PCy2,C2),28.0(d, 2 J CP =14.1Hz,PCy2,C2),27.6(dd,J CP =11.8,8.9 Hz,PCy2,C2),26.7–26.5 (m,PCy2,C4),22.4 (s,CH3,oTol) ppm. No PCP signal was observed. 31 P{ 1 H}NMR (162MHz, CD2Cl2): δ = 50.2 (d, 2 J PP =76.2Hz,P(Mor)3),34.0(d, 2 J PP =76.2Hz,PCy2)ppm. IR(ATR):2918(w),2847(w),1444(w),1251(m),1107(s),1081(m),1020(m), 997(w),950(s),917(m),846(w),732(m),707(m),589(w),497(m),473(m)cm -1 . Melting point: 246℃ (decomposition). 32 H 53 Elemental analysis of AuClN3O3P2: Calculated: C 46.75; H 6.50; N 5.11, Found: C 46.45; H 6.38; N 4.98.

[0581] L17-AuCl:

[0582]

[0583] The synthesis of L17AuCl was carried out according to the general procedure. Colorless crystals suitable for single crystal X-ray diffraction experiments were obtained by slow vapor diffusion of pentane into a saturated DCM solution of the compound. Yield: (92.0 mg, 0.114 mmol, 73%).

[0584] 1 H NMR (400MHz, CD2Cl2): δ=7.38–7.31(m,12H,Ph 邻位 + 间位 ),7.22–7.16(m,3H,Ph 对位 ),2.82(d, 3 J HP =8.2Hz,9H,CH3NPh),1.92–1.60(m,15H,PCy2,H1-4,PCPCH3),1.31–1.10(m,10H,PCy2,H2-4)ppm. 13 C{ 1 H}NMR (101MHz, CD2Cl2): δ = 146.9 (d, 2 J CP =3.6Hz,Ph 本位 ),129.5(s,Ph 间位 ),127.8(d, 3 J CP =2.9Hz,Ph 邻位 ),126.0(s,Ph 对位 ),42.3(d, 2 J CP =3.9Hz,CH3NPh),37.6(dd, 1 J CP =39.1Hz, 3 J CP =4.6Hz,PCy2,C1),31.8(d, 3 J CP =2.7Hz,PCy2,C3),31.4(s,PCy2,C3),27.9(d, 2 J CP =12.5Hz,PCy2,C2),27.5(d, 2 J CP =13.6Hz,PCy2,C2),26.6(d, 4 J CP =1.6Hz,),16.5(d, 2 J CP=8.0Hz,PCPCH3),13.8(dd, 1 J CP =213.4,68.8Hz,PCP)ppm. 31 P{ 1 H}NMR (162MHz, CD2Cl2): δ = 51.9 (d, 2 J PP =82.2Hz,P(PhNMe)3),38.2(d, 2 J PP =82.2Hz,PCy2)ppm. IR(ATR):2927(w),1490(m),1447(w),1261(w),1183(m),1058(m),1023(m), 909(s),883(s),775(m),767(m),700(s),555(m),539(s),517(w),464(w)cm -1 . Melting point: 208℃ (decomposition). 35 H 49 Elemental analysis of AuClN3P2: Calculated values: C 52.15; H 6.13; N 5.21, Found values: C 52.12; H 6.16; N 5.14.

[0585] L1-Rh(acac)CO:

[0586]

[0587] 30.0 mg (0.053 mmol) of L1 and 13.6 mg of Rh(acac)(CO)2 (0.053 mmol) were suspended in 0.5 ml of DCM and allowed to stand for 1 hour. Single crystals of L1-Rh(acac)CO were obtained by slowly diffusing pentane into the concentrated DCM solution.

[0588] 31 P NMR (162MHz, C6D6): δ = 52.5 (d, 2 J PP =78.9Hz,P + Pip3),39.5(dd, 1 J RhP =163.6Hz, 2 J PP =78.5.1Hz,PCy2).

[0589] L2-Rh(acac)CO:

[0590]

[0591] 25.0 mg (0.049 mmol) of L2 and 12.7 mg of Rh(acac)(CO)2 (0.049 mmol) were suspended in 0.5 ml of DCM and allowed to stand for 1 hour. Single crystals of L2-Rh(acac)CO were obtained by slowly diffusing pentane into the concentrated DCM solution.

[0592] 31 P NMR (162MHz, C6D6): δ = 62.4 (d, 2 J PP =84.1Hz,P + Pip3),39.4(br,PCy2).

[0593] L3-Rh(acac)CO:

[0594]

[0595] 25.0 mg (0.051 mmol) of L3 and 13.3 mg of Rh(acac)(CO)2 (0.051 mmol) were suspended in 0.5 ml of DCM and allowed to stand for 1 hour. Single crystals of L3-Rh(acac)CO were obtained by slowly diffusing pentane into the concentrated DCM solution.

[0596] 31 P NMR (162MHz, C6D6): δ = 77.8 (dd, 2 J PP =66.2Hz, 3 J RhP =4.7Hz,P + Pip3),39.4(dd, 2 J PP =66.2Hz, 1 J RhP =147.2Hz,PCy2).

[0597] L1-Rh(CO)2 cyclometallation:

[0598]

[0599] 30.0 mg (0.053 mmol) of L1 and 13.6 mg of Rh(acac)(CO)2 (0.053 mmol) were suspended in 0.5 ml of DCM and allowed to stand for 1 hour. Single crystals of L1-Rh(CO)2 were obtained by slowly diffusing pentane into the concentrated DCM solution.

[0600] 31 P NMR (162MHz, CD2Cl2): δ = 79.6 (dd, 2 JPRh =140.5Hz, 2 J PP =6.6Hz,PCy2),50.9(dd, 2 J PP =6.7Hz, 3 J RhP =10.6Hz,P + Pip3). 1 H NMR (400MHz, CD2Cl2) δ7.54 (d, J = 7.18Hzz), 6.71 (t, J = 7.49Hz, 1H), 6.63 (d, J = 7. 97Hz, 1H), 6.24 (td, J = 7.11, 1.39Hz, 1H), 3.59–2.67 (m, 14H), 2.15–1.18 (m, 48H). 13 C NMR(101MHz, CD2Cl2)δ195.81–192.02(m),165.52–164.97(m),145.29(d,J=3.82Hz),124.56,120.02(d,J=21.75Hz),115.92,48 .04, 38.91 (d, J = 26.31Hz), 32.70 (d, J = 2.93Hz), 30.40 (d, J = 4.40Hz), 27.21 (dd, J = 42.63, 12.51Hz), 26.24 (d, J = 4.12Hz), 24.67.

[0601] L1-Ir(COD) cyclometalation:

[0602]

[0603] 20.0 mg (0.035 mmol) of L1 and 11.8 mg of [Ir(COD)Cl]2 (0.018 mmol) were suspended in 0.5 ml of THF and allowed to stand for 1 hour. Single crystals of L1-Ir(COD) were obtained by slowly diffusing pentane into the concentrated THF solution.

[0604] 31 P NMR (162MHz, THF): δ = 55.2 (d, 2 J PP =6.4Hz,PCy2),54.6(dd, 2 J PP =6.3Hz,P + Pip3).

[0605] L2-Ni (benzaldehyde):

[0606]

[0607] 200mg (0.394mmol) L2 and 108mg Ni (COD) 2 (0.394mmol) are suspended in 4ml hexane, 0.08ml benzaldehyde (0.78g, 2 equivalents) is added, and the reaction mixture is stirred for 30 minutes. An orange solid is precipitated, filtered out and washed with 3 × 4ml hexanes, and dried in a vacuum. 83.6mg (0.194mmol, 49.1%) complexes are obtained as orange solids. By slowly diffusing pentane into a concentrated solution of THF, L2-Ni (benzaldehyde) single crystals are obtained.

[0608] 31 P NMR (162MHz, THF): δ = 72.2 (d, 2 J PP =116.2Hz,PCy2),26.8(dd, 2 J PP =116.2Hz,P + Pip3).

[0609] Comparison with the catalyst shown in WO 2019 / 030304

[0610] Monoarylation of acetone

[0611]

[0612]

[0613] Monoarylation of ammonia

[0614]

[0615]

Claims

1. A ligand of formula 1, wherein R1 is each unsubstituted or substituted alkyl, perfluoroalkyl, aryl or cycloalkyl; cyano; sulfonyl-SO2-R10, wherein R10 = C1-C5 alkyl, C5-C6 cycloalkyl, C5-C10 aryl, each unsubstituted or substituted by C1-C4 alkyl or C1-C4 perfluoroalkyl; silyl-Si(R20R30R40), wherein R20, R30 and R40 are each independently C1-C6 alkyl or C5-C10 aryl, each unsubstituted or substituted by C1-C4 alkyl; R2 is independently substituted or unsubstituted alkyl, cycloalkyl, adamantyl or aryl; R3, R4 and R5 are each alkyl, cycloalkyl or aryl, which may be unsubstituted or substituted; or at least two of R3, R4 and R5 are alkyl or alkyl ether bridges and together with the phosphorus atom form a heterocyclic ring, or wherein R3 and R6 and / or R4 and R7 and / or R5 and R8 together form an alkyl or alkyl ether bridge, which together with the nitrogen atom to which they are attached form a heterocyclic ring; R6, R7 and R8 are alkyl or aryl groups which may be unsubstituted or substituted, or individually or collectively form a heterocyclic ring with R3, R4 or R5 and the nitrogen atom to which they are attached; m, n and o are 0 or 1, provided that at least one of m, n and o is 1.

2. The ligand according to claim 1 , wherein R1 is selected from C1 to C9 alkyl; C4-C8 cycloalkyl; C5-C10 aryl; cyano; sulfonyl-SO2-R10, wherein R10 = C1-C5 alkyl, C5-C6 cycloalkyl, C5-C10 aryl, each unsubstituted or substituted by one or more C1 to C4 alkyl, C1 to C4 alkoxy or C1 to C4 perfluoroalkyl; silyl-Si(R20R30R40), wherein each of R20, R30 and R40 is independently C1-C6 alkyl or C5-C10 aryl, each unsubstituted or substituted by C1-C4 alkyl, or R1 is C5-C10 aryl, which may be substituted one or more times by C1 to C5 alkyl, C1 to C5 alkoxy or C1 to C5 perfluoroalkyl.

3. The ligand according to claim 1, wherein R2 is a C1 to C9 alkyl group, a C4-C8 cycloalkyl group, an adamantyl group, a C5 to C10 aryl group, which may be unsubstituted or substituted with one or more C1 to C5 alkyl groups, C1 to C5 alkoxy groups or C1 to C5 perfluoroalkyl groups.

4. The ligand according to claim 1 , wherein R3, R4 and R5 are independently C1 to C9 alkyl, C4-C8 cycloalkyl, adamantyl, C5 to C10 aryl, which may be unsubstituted or substituted by C1 to C5 alkyl, C1 to C5 alkoxy or C1 to C5 perfluoroalkyl; or at least two of R3, R4 and R5 are C2 to C10 alkyl, C2 to C10 alkenyl or C2 to C10 alkyl ether bridge, and together with the phosphorus atom form a heterocycle.

5. The ligand according to claim 1 , wherein R3, R4 and R5 are independently C1 to C5 alkyl, C4-C8 cycloalkyl, adamantyl, C5 to C6 aryl, which may be unsubstituted or substituted by C1 to C5 alkyl, C1 to C5 alkoxy or C1 to C5 perfluoroalkyl; or at least two of R3, R4 and R5 are C2 to C5 alkyl, C2 to C5 alkenyl or C2 to C4 alkyl ether bridge, and together with the phosphorus atom form a heterocycle.

6. The ligand of claim 1 , wherein at least two of R3, R4 and R5 together are C2 to C8 alkyl or C2 to C8 alkyl ether bridge, which is optionally substituted with one or more C1 to C5 alkyl or cycloalkyl groups; or the C2 to C8 alkyl or C2 to C8 alkyl ether bridge is part of a fused C4 to C8 cycloalkyl ring, forming a heterocycle with the phosphorus atom.

7. R6, R7 and R8 are C1 to C9 alkyl or C5 to C10 aryl, which may be unsubstituted or substituted by one or more C1 to C5 alkyl, C1 to C5 alkoxy or C1 to C5 perfluoroalkyl; or form a heterocycle individually or collectively with R3, R4 or R5 and the nitrogen atom to which they are attached.

8. The ligand of claim 1 , wherein R3 and R6 and / or R4 and R7 and / or R5 and R8 together are a C2 to C8 alkyl group or a C2 to C8 alkyl ether bridge, which is optionally substituted with one or more C1 to C5 groups, or the C2 to C8 alkyl group or C2 to C8 alkyl ether bridge is part of a fused C4 to C8 cycloalkyl ring, forming a heterocycle together with the nitrogen atom to which it is attached.

9. The ligand according to claim 1, wherein R1 represents a C1 to C9 alkyl group, a C4-C8 cycloalkyl group, a C5-C10 aryl group, and the aryl group may be unsubstituted or substituted by a C1 to C5 alkyl group, a C1 to C5 alkoxy group or a C1 to C5 perfluoroalkyl group.

10. The ligand of claim 1 , wherein R is selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-pentyl (pentyl), 2-pentyl (sec-pentyl), 3-pentyl, 2-methylbutyl, 3-methylbutyl (isopentyl / iso-amyl), 3-methylbutan-2-yl, 2-methylbutan-2-yl, 2,2-dimethylpropyl (neopentyl), n-hexyl, trifluoromethyl, cyclobutyl, cyclopentyl, cyclohexyl, menthyl, phenyl, o-toluoyl, naphthyl, o-methoxyphenyl, o-ethoxyphenyl, di-(o-methoxy)phenyl, p-trifluoromethylphenyl, trimethylsilyl, triisopropyl-silyl, tri-tert-butylsilyl, cyano, methylsulfonyl, toluoylsulfonyl, and trifluoromethylsulfonyl.

11. The ligand according to claim 1, wherein R2 is selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-pentyl (pentyl), 2-pentyl (sec-pentyl), 3-pentyl, 2-methylbutyl, 3-methylbutyl (isopentyl), 3-methylbutan-2-yl, 2-methylbutan-2-yl, 2,2-dimethylpropyl (neopentyl), n-hexyl, trifluoromethyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, phenyl, o-methylphenyl, m-methylphenyl or p-methylphenyl, naphthyl.

12. The ligand according to claim 1, wherein R3, R4, R5, R6, R7 and R8 are independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentylbutyl, n-pentyl, n-pentyl (pentyl), 2-pentyl (sec-pentyl), 3-pentyl, 2-methylbutyl, 3-methylbutyl (isopentyl), 3-methylbutan-2-yl, 2-methylbutan-2-yl, 2,2-dimethylpropyl (neopentyl), n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, mesityl. The ligand according to claim 1 , wherein at least two of m, n and o are 1. The ligand according to claim 1 , wherein all of m, n and o are 1.

15. The ligand according to claim 1, wherein R1 is C1 to C9 alkyl, C5-C10 aryl, each unsubstituted or substituted by C1 to C4 alkyl; sulfonyl-SO2-R10, wherein R10 = C5-C10 aryl, each unsubstituted or substituted by C1 to C4 alkyl; R2 is C1 to C9 alkyl, C4 to C8 cycloalkyl or adamantyl; R3, R4 and R5 are independently C1 to C9 alkyl, C4 to C8 cycloalkyl, adamantyl, C5 to C10 aryl; R6, R7 and R8 are C1 to C9 alkyl or C5 to C10 aryl, which may be unsubstituted or substituted with one or more C1 to C5 alkyl groups; and / or wherein R3 and R6 and / or R4 and R7 and / or R5 and R8 together are C2 to C8 alkyl or a C2 to C8 alkyl ether bridge, optionally the C2 to C8 alkyl bridge may be partly or fully part of a fused C4 to C8 cycloalkyl ring.

16. The ligand according to claim 1, wherein R1 is C1 to C9 alkyl, C5-C10 aryl, each unsubstituted or substituted by C1 to C4 alkyl; sulfonyl-SO2-R10, wherein R10 = C5-C10 aryl, each unsubstituted or substituted by C1 to C4 alkyl; R2 is C1 to C9 alkyl, C4 to C8 cycloalkyl or adamantyl; At least two of m, n and o are 1; At least two of R3, R4 and R5 together are C2 to C8 alkyl or C2 to C8 alkyl ether bridge, which is optionally substituted with one or more C1 to C5 alkyl or cycloalkyl groups; or the C2 to C8 alkyl or C2 to C8 alkyl ether bridge is part of a fused C4 to C8 cycloalkyl ring, forming a heterocyclic ring with the phosphorus atom; R6, R7 and / or R8 are C1 to C6 alkyl or C5-C10 aryl, which are unsubstituted or substituted with one or more C1 to C5 alkyl groups; Provided that if one of R3, R4 and R5 is not a C2-C8 alkyl bridge or a C2-C8 alkyl ether bridge, then it is a C4-C8 cycloalkyl or adamantyl group.

17. The ligand according to claim 1, wherein R1 is C1 to C9 alkyl, C5-C10 aryl, each unsubstituted or substituted by C1 to C4 alkyl; sulfonyl-SO2-R10, wherein R10 = C5-C10 aryl, each unsubstituted or substituted by C1 to C4 alkyl; R2 is C1 to C9 alkyl, C4 to C8 cycloalkyl or adamantyl; R3, R4 and R5 are independently C1 to C9 alkyl, C4 to C8 cycloalkyl, adamantyl, C5 to C10 aryl; R6, R7 and R8 are C1 to C9 alkyl or C5 to C10 aryl, which may be unsubstituted or substituted with one or more C1 to C5 alkyl groups; and / or wherein R3 and R6 and / or R4 and R7 and / or R5 and R8 together are C2 to C8 alkyl or a C2 to C8 alkyl ether bridge, optionally the C2 to C8 alkyl bridge may be partly or fully part of a fused C4 to C8 cycloalkyl ring.

18. The ligand according to claim 1, wherein R1 is C1 to C9 alkyl or C5-C10 aryl, each unsubstituted or substituted with one or more C1 to C4 alkyl groups; R2 is C1 to C9 alkyl, C4 to C8 cycloalkyl or adamantyl; m is 0, n and o are 1; R3 is C4-C8 cycloalkyl or adamantyl; R4 and R5 together are C2 to C8 alkyl or C2 to C8 alkyl ether bridges forming a heterocyclic ring with the phosphorus atom, said C2 to C8 alkyl or C2 to C8 alkyl ether bridge being optionally substituted with one or more C1 to C5 alkyl groups; or said C2 to C8 alkyl or C2 to C8 alkyl ether bridge is part of a fused C4 to C8 cycloalkyl ring in whole or in part; R7 and R8 are C1 to C9 alkyl or C5 to C10 aryl, which may be unsubstituted or substituted with one or more C1 to C5 alkyl groups.

19. A ligand of formula 1, wherein R1 is C1 to C9 alkyl or C5-C10 aryl, each unsubstituted or substituted with one or more C1 to C4 alkyl groups; R2 is C1 to C9 alkyl, C4 to C8 cycloalkyl or adamantyl; m, n, and o are 1; and R3, R4 and R5 are independently C1 to C9 alkyl, C4 to C8 cycloalkyl or C5 to C10 aryl; R6, R7 and R8 are C1 to C9 alkyl or C5 to C10 aryl, which may be unsubstituted or substituted with one or more C1 to C5 alkyl groups.

20. A ligand of formula 1, wherein R1 is C1 to C9 alkyl or C5-C10 aryl, each unsubstituted or substituted with one or more C1 to C4 alkyl groups; R2 is C1 to C9 alkyl, C4 to C8 cycloalkyl or adamantyl; m, n, and o are 1; and Each pair of R3 and R6, R4 and R7, R5 and R8 together is a C2 to C8 alkyl bridge or a C2 to C8 alkyl ether bridge, optionally the C2 to C8 alkyl bridge may be part of a fused C4 to C8 cycloalkyl ring in part or in whole.

21. A ligand of formula 1, wherein R1 is selected from methyl, isopropyl, phenyl, and o-tolyl.

22. A ligand of formula 1, wherein R2 is selected from methyl, isopropyl, tert-butyl, cyclohexyl, phenyl and adamantyl.

23. A ligand of formula 1, wherein R3, R4 and R5 are methyl, phenyl or mesityl.

24. A ligand of formula 1, wherein one or more of R6, R7 and R8 is methyl, isopropyl, isopentyl, neopentyl, phenyl, mesityl.

25. The ligand of claim 1, wherein R3 and R6 and / or R4 and R7 and / or R5 and R8 together with the nitrogen atom to which they are attached form a piperidinyl or morpholinyl ring.

26. The ligand of claim 1, wherein R3 and R6 and R4 and R7 and R5 and R8 together with the nitrogen atom to which they are attached form a piperidinyl or morpholinyl ring. 27 . A metal complex comprising a transition metal and a ligand according to claim 1 , and optionally comprising at least one organic ligand L and / or at least one halogen X.

28. A method for performing a coupling reaction, comprising the steps of: - providing a reaction mixture comprising at least a substrate, a coupling partner and a metal complex comprising a ligand according to any one of claims 1 to 26; and - reacting the substrate with the coupling partner in the presence of the metal complex or a derivative thereof to form a coupling product.

29. The method for performing a coupling reaction according to claim 28, wherein the metal complex comprising a ligand is the metal complex according to claim 27.

30. The method according to one or more of claims 29 to 30, wherein the coupling reaction can be selected from the group consisting of: (i) Catalytic hydrofunctionalization of alkynes and alkenes; (ii) Catalytic hydroamination of alkynes and alkenes; (iii) catalytic OH addition reactions of alkynes and alkenes; (iv) catalyzing coupling reactions; (v) catalyzed Kumada coupling reaction, Murahashi coupling reaction, Negishi coupling reaction or Suzuki coupling reaction, especially for the production of biarylene; (vi) catalyzing cross-coupling reactions, in particular CN and CO coupling reactions; and / or (vii) Catalysis of Heck coupling reactions, particularly for the preparation of arylated alkenes, and Sonogashira coupling reactions, particularly for the preparation of arylated and olefinated alkynes. (viii) Catalytic α-arylation of carbonyl compounds and imines.

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