Mixed P,N-donor ligands, their complexes, and uses thereof

Abstract

The present invention relates to novel ligands of formula 1, their metal complexes and their use for catalytic purposes. In Formula 1, R1 is alkyl, perfluoroalkyl, aryl, or cycloalkyl, each of which is unsubstituted or substituted with cyano, sulfonyl: -SO2-R10 (R10 = C1-C5 alkyl, C5-C6 cycloalkyl, C5-C10 aryl, each of which is unsubstituted or substituted with C1-C4 alkyl or C1-C4 perfluoroalkyl), or silyl: Si(R20R30R40) (R20, R30, and R40 are, independently of one another, C1-C6 alkyl or C5-C10 aryl, each of which is unsubstituted or substituted with C1-C4 alkyl); R2 is alkyl, cycloalkyl, adamantyl, or aryl, each of which is substituted or unsubstituted; and R3, R4, and R5 are alkyl, cycloalkyl, or aryl. R3 and R6, and / or R4 and R7, and / or R5 and R8 together form an alkyl bridge or alkyl ether bridge which, together with the nitrogen atom to which they are attached, forms a heterocyclyl ring; R6, R7, and R8 are alkyl or aryl which are unsubstituted or substituted, or which, individually or collectively, form a heterocyclyl ring 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.

Description

[Technical Field]

[0001] Mixed P,N-donor ligands, their complexes, and uses thereof. [Background technology]

[0002] Many organometallic compounds, especially those of transition and noble metals, 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 synthetic organic chemistry. Nevertheless, there is a constant need for new catalysts that meet specific requirements or have new properties to extend and complement the scope of synthetic chemistry.

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

[0004] WO 2019 / 030304 shows the use of novel ligands for preparing metal complexes and their use in organometallic catalysis. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2017 / 093427 [Patent Document 2] International Publication No. 2019 / 030304 Summary of the Invention [Means for solving the problem]

[0006] It has now been discovered that a new type of nitrogen- and phosphorus-containing ligand is surprisingly capable of forming new, previously unknown, and catalytically active metal complexes, particularly compounds of transition metals.

[0007] These compounds are ligands of general formula 1: [ka]

[0008] During the ceremony, R1 is each substituted or unsubstituted alkyl, perfluoroalkyl, aryl or cycloalkyl, cyano, or sulfonyl: -SO2-R10 (R10 = C1-C5 alkyl, C5-C6 cycloalkyl, C5-C10 aryl), where each of the R1 is unsubstituted or substituted with C1-C4 alkyl or C1-C4 perfluoroalkyl; or silyl: Si(R20R30R40), where R20, R30, and R40 are each independently C1-C6 alkyl or C5-C10 aryl, where each is unsubstituted or substituted with C1-C4 alkyl; R2 is alkyl, cycloalkyl, adamantyl, or aryl, each of which is substituted or unsubstituted; R3, R4, and R5 are alkyl, cycloalkyl, or aryl, each of which is unsubstituted or substituted, or at least two of R3, R4, and R5 are alkyl or alkyl ether bridges which, together with the phosphorus atom, form a heterocyclyl ring; R3 and R6, and / or R4 and R7, and / or R5 and R8, together are an alkyl bridge or an alkyl ether bridge, which, together with the nitrogen atom to which they are attached, form a heterocyclyl ring; R6, R7, and R8 are alkyl or aryl, which are unsubstituted or substituted, or which individually or collectively form a heterocyclyl ring with R3, R4, or R5 and the nitrogen atom to which they are attached; A ligand in which m, n, and o are 0 or 1, with the proviso that at least one of m, n, and o is 1.

[0009] The present invention also relates to metal complexes, particularly transition metal and noble metal complexes, which comprise at least one ligand of formula 1.

[0010] The present invention also relates to methods of carrying out coupling reactions involving such complexes, which may be isolated prior to use in the coupling reaction, or which may be used in a one-pot reaction without isolating such complexes.

[0011] As shown in the examples, each of the ligands of the present invention, and complexes containing such ligands, are effective in enabling coupling reactions. Although nitrogen substitution results in significant differences that are not always predictable, the ligands exhibit the following behavior quite different from their alkyl / aryl analogs:

[0012] 1) Structural Aspects / Stability: The introduction of nitrogen causes the ligand of formula 1 to react primarily as a P,N ligand, rather than as a simple monophosphane. Some complexes exhibit N-coordination that would not be possible without the nitrogen. This N-coordination naturally also influences the reaction, so Pd(0)dba complexes with the ligand of formula 1 are significantly more stable.

[0013] 2) Scope of variation: The wide range of aminophosphanes readily prepared from PCl3 and simple amines makes it easier to generate a broader spectrum of ligands of Formula 1 than alkyl and aryl substituents. This allows for easier control of the steric properties of the nitrogen and its binding capacity.

[0014] 3) Reactivity: As mentioned above, the ligands of formula 1 behave significantly differently from their alkyl / aryl analogs. Therefore, for many applications, activity is likely lower because the complexes are more stable. However, there are advantages when further tuning is required. The best example to date is the monoarylation of acetone, which showed very poor selectivity with the YPhos ligand shown in WO 2019 / 030304. However, with the ligands of formula 1, excellent selectivity and yield are possible, and the catalysts are one of the best catalysts for this reaction described in the literature to date.

[0015] 1. A ligand of formula 1,

[0016] [ka]

[0017] wherein R1 is each substituted or unsubstituted alkyl, perfluoroalkyl, aryl or cycloalkyl, cyano, sulfonyl: -SO2-R10 (R10 = C1-C5 alkyl, C5-C6 cycloalkyl, C5-C10 aryl) (each of the above R1 is unsubstituted or substituted with C1-C4 alkyl or C1-C4 perfluoroalkyl); or silyl: Si(R20R30R40) (R20, R30, and R40 are each independently C1-C6 alkyl or C5-C10 aryl, each unsubstituted or substituted with C1-C4 alkyl); R2 is alkyl, cycloalkyl, adamantyl, or aryl, each of which is substituted or unsubstituted; R3, R4, and R5 are alkyl, cycloalkyl, or aryl, each of which is unsubstituted or substituted, or at least two of R3, R4, and R5 are alkyl bridges or alkyl ether bridges which, together with the phosphorus atom, form a heterocyclyl ring; R3 and R6, and / or R4 and R7, and / or R5 and R8 together form an alkyl bridge or an alkyl ether bridge which, together with the nitrogen atom to which they are attached, forms a heterocyclyl ring; R6, R7, and R8 are alkyl or aryl, which are unsubstituted or substituted, or which individually or collectively form a heterocyclyl ring with R3, R4, or R5 and the nitrogen atom to which they are attached; A ligand wherein m, n, and o are 0 or 1, with the proviso that at least one of m, n, and o is 1.

[0018] 2. The ligand of item 1, wherein R1 is selected from C1-C9 alkyl, C4-C8 cycloalkyl, C5-C10 aryl, cyano, sulfonyl; -SO2-R10 (where R10 = C1-C5 alkyl, C5-C6 cycloalkyl, C5-C10 aryl), each of which is unsubstituted or substituted with one or more C1-C4 alkyl, C1-C4 alkoxy, C1-C4 perfluoroalkyl; and is silyl-:Si(R20R30R40) (each of R20, R30, and R40 is independently C1-C6 alkyl, or C5-C10 aryl, each unsubstituted or substituted with C1-C4 alkyl), or R1 is C5-C10 aryl, optionally substituted one or more times with C1-C5 alkyl, C1-C5 alkoxy, or C1-C5 perfluoroalkyl, ligand.

[0019] 3. A ligand according to any of the preceding paragraphs, wherein R2 is C1-C9 alkyl, C4-C8 cycloalkyl, adamantyl, C5-C10 aryl, which may be unsubstituted or substituted with one or more C1-C5 alkyl, C1-C5 alkoxy, or C1-C5 perfluoroalkyl.

[0020] 4. A ligand according to any of the preceding paragraphs, wherein R3, R4, and R5 are, independently of one another, C1-C9 alkyl, C4-C8 cycloalkyl, adamantyl, C5-C10 aryl, which are unsubstituted or substituted with C1-C5 alkyl, C1-C5 alkoxy, or C1-C5 perfluoroalkyl, or at least two of R3, R4, and R5 are C2-C10 alkyl, a C2-C10 alkenyl bridge, or a C2-C10 alkyl ether bridge, which, together with the phosphorus atom, form a heterocyclyl ring.

[0021] 5. A ligand according to any of the preceding paragraphs, wherein R3, R4, and R5 are, independently of one another, C1-C5 alkyl, C4-C8 cycloalkyl, adamantyl, C5-C6 aryl, which are unsubstituted or substituted with C1-C5 alkyl, C1-C5 alkoxy, or C1-C5 perfluoroalkyl, or at least two of R3, R4, and R5 are C2-C5 alkyl bridges, C2-C5 alkenyl bridges, or C2-C4 alkyl ether bridges, which, together with the phosphorus atom, form a heterocyclyl cyclic ring.

[0022] 6. A ligand according to any of the preceding paragraphs, wherein at least two of R3, R4, and R5, taken together, are a C2-C8 alkyl bridge or a C2-C8 alkyl ether bridge, which may be optionally substituted with one or more C1-C5 alkyl or cycloalkyl groups, or the C2-C8 alkyl bridge or C2-C8 alkyl ether bridge may be part of a fused C4-C8 cycloalkyl ring, forming a heterocyclyl cyclic ring with the phosphorus atom.

[0023] 7. A ligand according to any of the preceding paragraphs, wherein R6, R7, and R8 are C1-C9 alkyl or C5-C10 aryl, which are unsubstituted or substituted with one or more C1-C5 alkyl, C1-C5 alkoxy, or C1-C5 perfluoroalkyl, or which individually or collectively form a heterocyclyl ring with R3, R4, or R5 and the nitrogen atom to which they are attached.

[0024] 8. A ligand according to any of the preceding paragraphs, wherein R3 and R6, and / or R4 and R7, and / or R5 and R8 together are a C2-C8 alkyl bridge or a C2-C8 alkyl ether bridge, which may optionally be substituted with one or more C1-C5 groups, or the C2-C8 alkyl bridge or the C2-C8 alkyl ether bridge are part of a fused C4-C8 cycloalkyl ring, which, together with the nitrogen atom to which they are attached, may form a heterocyclyl ring.

[0025] 9. A ligand according to any of the preceding paragraphs, wherein R1 represents C1-C9 alkyl, C4-C8 cycloalkyl, or C5-C10 aryl, wherein the aryl is unsubstituted or substituted with C1-C5 alkyl, C1-C5 alkoxy, or C1-C5 perfluoroalkyl.

[0026] 10. A ligand according to any of the preceding paragraphs, wherein R1 is selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-pentyl (amyl), 2-pentyl (sec-pentyl), 3-pentyl, 2-methylbutyl, 3-methylbutyl (iso-pentyl or iso-amyl), 3-methylbut-2-yl, 2-methylbut-2-yl, 2,2-dimethylpropyl (neopentyl), n-hexyl, trifluoromethyl, cyclobutyl, cyclopentyl, cyclohexyl, menthyl, phenyl, o-toluyl, naphthyl, o-methoxyphenyl, o-ethoxyphenyl, di-(o-methoxy)phenyl, p-trifluoromethylphenyl, trimethylsilyl, triisopropyl-silyl, tri-tert-butylsilyl, cyano, methylsulfonyl, toluenesulfonyl, and trifluoromethylsulfonyl.

[0027] 11. A ligand according to any of the preceding paragraphs, wherein R2 is selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-pentyl (amyl), 2-pentyl (sec-pentyl), 3-pentyl, 2-methylbutyl, 3-methylbutyl (isopentyl or isoamyl), 3-methylbut-2-yl, 2-methylbut-2-yl, 2,2-dimethylpropyl (neopentyl), n-hexyl, trifluoromethyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, phenyl, o-, m-, or p-methylphenyl, naphthyl.

[0028] 12. A ligand according to any of the preceding paragraphs, 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(amyl), 2-pentyl(sec-pentyl), 3-pentyl, 2-methylbutyl, 3-methylbutyl(iso-pentyl or iso-amyl), 3-methylbut-2-yl, 2-methylbut-2-yl, 2,2-dimethylpropyl(neopentyl), n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, mesityl.

[0029] 13. A ligand according to any of the preceding paragraphs, wherein at least two or at least one of m, n, and o is 1.

[0030] 14. A ligand according to any preceding item, wherein all of m, n, and o are 1.

[0031] 15. A ligand according to any of the preceding paragraphs, R1 is C1-C9 alkyl or C5-C10 aryl (each of which is unsubstituted or substituted with C1-C4 alkyl), or sulfonyl: -SO2-R10 (R10 = C5-C10 aryl, which is unsubstituted or substituted with C1-C4 alkyl); R2 is C1-C9 alkyl, C4-C8 cycloalkyl, or adamantyl; R3, R4, and R5 are, independently of one another, C1-C9 alkyl, C4-C8 cycloalkyl, adamantyl, or C5-C10 aryl; R6, R7, and R8 are C1-C9 alkyl or C5-C10 aryl, which are unsubstituted or substituted with one or more C1-C5 alkyls; and / or Ligands in which R3 and R6, and / or R4 and R7, and / or R5 and R8, taken together, are a C2-C8 alkyl bridge, or a C2-C8 alkyl ether bridge, optionally wherein said C2-C8 alkyl bridge is part or all of a fused C4-C8 cycloalkyl ring.

[0032] 16. A ligand according to any of the preceding paragraphs, R1 is C1-C9 alkyl or C5-C10 aryl (each of which is unsubstituted or substituted with C1-C4 alkyl), or sulfonyl: -SO2-R10 (R10 = C5-C10 aryl, which is unsubstituted or substituted with C1-C4 alkyl); R2 is C1-C9 alkyl, C4-C8 cycloalkyl, or adamantyl; at least two of m, n, and o are 1; at least two of R3, R4, and R5 together are a C2-C8 alkyl bridge, or a C2-C8 alkyl ether bridge, which may optionally be substituted with one or more C1-C5 alkyl or cycloalkyl groups, or the C2-C8 alkyl bridge or C2-C8 alkyl ether bridge is part of a fused C4-C8 cycloalkyl ring, which together with the phosphorus atom forms a heterocyclyl ring; R6, R7, and / or R8 are C1-C6 alkyl or C5-C10 aryl, which are unsubstituted or substituted with one or more C1-C5 alkyls; with the proviso that when 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 ligand.

[0033] 17. A ligand according to any of the preceding paragraphs, R1 is C1-C9 alkyl or C5-C10 aryl (each of which is unsubstituted or substituted with C1-C4 alkyl), or sulfonyl: -SO2-R10 (R10 = C5-C10 aryl, which is unsubstituted or substituted with C1-C4 alkyl); R2 is C1-C9 alkyl, C4-C8 cycloalkyl, or adamantyl; R3, R4, and R5 are, independently of one another, C1-C9 alkyl, C4-C8 cycloalkyl, adamantyl, or C5-C10 aryl; R6, R7, and R8 are C1-C9 alkyl or C5-C10 aryl, which are unsubstituted or substituted with one or more C1-C5 alkyls; and / or Ligands in which R3 and R6, and / or R4 and R7, and / or R5 and R8, taken together, are a C2-C8 alkyl bridge, or a C2-C8 alkyl ether bridge, optionally wherein said C2-C8 alkyl bridge is part or all of a fused C4-C8 cycloalkyl ring.

[0034] 18. A ligand according to any of the preceding paragraphs, R1 is C1-C9 alkyl or C5-C10 aryl, each of which is unsubstituted or substituted with one or more C1-C4 alkyl; R2 is C1-C9 alkyl, C4-C8 cycloalkyl, or adamantyl; m is 0, n and o are 1, R3 is C4-C8 cycloalkyl or adamantyl; R4 and R5 are together a C2-C8 alkyl bridge or a C2-C8 alkyl ether bridge forming a heterocyclyl ring with the phosphorus atom, said C2-C8 alkyl bridge or C2-C8 alkyl ether bridge optionally being substituted with one or more C1-C5 alkyl groups, or said C2-C8 alkyl bridge or C2-C8 alkyl ether bridge being part of a fully or partially fused C4-C8 cycloalkyl ring; A ligand in which R7 and R8 are C1-C9 alkyl, or C5-C10 aryl, which is unsubstituted or substituted with one or more C1-C5 alkyl.

[0035] 19. A ligand according to any of the preceding paragraphs, R1 is C1-C9 alkyl or C5-C10 aryl, each of which is unsubstituted or substituted with one or more C1-C4 alkyl; R2 is C1-C9 alkyl, C4-C8 cycloalkyl, or adamantyl; m, n, and o are 1; R3, R4, and R5 are each independently C1-C9 alkyl, C4-C8 cycloalkyl, or C5-C10 aryl, and R6, R7, and R8 are C1-C9 alkyl or C5-C10 aryl, which are unsubstituted or substituted with one or more C1-C5 alkyls.

[0036] 20. A ligand according to any of the preceding paragraphs, R1 is C1-C9 alkyl or C5-C10 aryl, each of which is unsubstituted or substituted with one or more C1-C4 alkyl; R2 is C1-C9 alkyl, C4-C8 cycloalkyl, or adamantyl; m, n, and o are 1; A ligand in which each pair of R3 and R6, R4 and R7, and R5 and R8 taken together is a C2-C8 alkyl bridge, or a C2-C8 alkyl ether bridge, and optionally the C2-C8 alkyl bridge may be part or all of a fused C4-C8 cycloalkyl ring.

[0037] 21. A ligand according to any of the preceding items, wherein R1 is selected from methyl, isopropyl, phenyl, and o-tolyl.

[0038] 22. A ligand according to any of the preceding paragraphs, wherein R2 is selected from methyl, isopropyl, tert-butyl, cyclohexyl, phenyl, and adamantyl.

[0039] 23. A ligand according to any of the preceding items, wherein R3, R4, and R5 are methyl, phenyl, or mesityl.

[0040] 24. A ligand according to any of the preceding paragraphs, wherein one or more of R6, R7, and R8 is methyl, isopropyl, isopentyl, neopentyl, phenyl, mesityl.

[0041] 25. A ligand according to any of the preceding paragraphs, 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 ring or a morpholinyl ring.

[0042] 26. A ligand according to any of the preceding items, wherein R3 and R6, R4 and R7, and R5 and R8, together with the nitrogen atom to which they are attached, form a piperidinyl or morpholinyl ring.

[0043] 27. A metal complex comprising a transition metal and a ligand according to any one of items 1 to 26, optionally comprising at least one organic ligand L and / or at least one halogen X.

[0044] 28. The metal complex according to item 27, wherein the transition metal is a noble metal.

[0045] 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, and in particular, selected from the group consisting of rhodium, iridium, palladium, and gold.

[0046] 30. The metal complex according to any one of items 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.

[0047] 31. The metal complex according to any one of items 27 to 30, wherein the halogen is chlorine or bromine.

[0048] 32. A method for carrying out 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 items 1 to 26; - reacting said substrate with said coupling partner in the presence of a metal complex or a derivative thereof to form a coupling product.

[0049] 33. A method for carrying out a coupling reaction according to claim 32, wherein the metal complex containing a ligand is a metal complex according to any one of items 27 to 31.

[0050] 34. The method according to one or more of items 32 or 33, wherein the substrate is a substituted aromatic compound.

[0051] 35. The method according to item 34, wherein the substituted aromatic compound is an aromatic compound or a heteroaromatic compound.

[0052] 36. The method according to item 34 or 35, wherein the substituted aromatic compound is substituted with a leaving group, and / or an unsaturated aliphatic group, or a leaving group.

[0053] 37. The method according to item 36, wherein the leaving group is selected from the group consisting of halogen, triflate, tosylate, nosylate, and mesylate, and / or the unsaturated aliphatic group is selected from the group consisting of an alkene or alkyne, particularly having 2 to 12, especially 2 to 8, carbon atoms.

[0054] 38. The method according to one or more of the preceding items, wherein the coupling partner is an organometallic compound.

[0055] 39. The method according to item 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 compounds.

[0056] 40. The method of claim 38 or 39, wherein the organometallic compound contains at least one aromatic group.

[0057] 41. The method according to item 38 or 39, wherein the organometallic compound contains at least one unsaturated aliphatic group.

[0058] 42. The method according to item 38 or 39, wherein the organometallic compound contains at least one saturated aliphatic group.

[0059] 43. The coupling reaction is selected from the group consisting of: (i) catalytic hydrofunctionalization of alkynes and alkenes; (ii) catalytic hydroamination of alkynes and alkenes; (iii) catalytic OH addition to alkynes and alkenes; (iv) catalytic coupling reactions, (v) catalytic Kumada, Murahashi, Negishi, or Suzuki coupling reactions, especially for the formation of biarylenes; (vi) catalytic cross-coupling reactions, in particular CN and CO coupling reactions, and / or (vii) catalytic Heck coupling reactions, particularly for the preparation of arylated olefins, and Sonogashira coupling reactions, particularly for the preparation of arylated and alkenylated alkynes; (vii) catalytic α-arylation of carbonyl compounds and imines; 43. The method according to one or more of items 32 to 42, selected from: DETAILED DESCRIPTION OF THE INVENTION

[0060] Detailed Description of the Invention

[0061] The present invention provides a ligand of formula 1,

[0062] [ka]

[0063] wherein R1 is each substituted or unsubstituted alkyl, perfluoroalkyl, aryl or cycloalkyl, cyano, sulfonyl: -SO2-R10 (R10 = C1-C5 alkyl, C5-C6 cycloalkyl, C5-C10 aryl) (each of the above R1 is unsubstituted or substituted with C1-C4 alkyl or C1-C4 perfluoroalkyl); or silyl: Si(R20R30R40) (R20, R30, and R40 are each independently C1-C6 alkyl or C5-C10 aryl, each unsubstituted or substituted with C1-C4 alkyl); R2 is alkyl, cycloalkyl, adamantyl, or aryl, each of which is substituted or unsubstituted; R3, R4, and R5 are alkyl, cycloalkyl, or aryl, each of which is unsubstituted or substituted, or at least two of R3, R4, and R5 are alkyl bridges or alkyl ether bridges which, together with the phosphorus atom, form a heterocyclyl ring; R3 and R6, and / or R4 and R7, and / or R5 and R8 together form an alkyl bridge or an alkyl ether bridge which, together with the nitrogen atom to which they are attached, forms a heterocyclyl ring; R6, R7, and R8 are alkyl or aryl, which may be unsubstituted or substituted, or may individually or collectively form a heterocyclyl ring with R3, R4, or R5 and the nitrogen atom to which they are attached; and m, n, and o are 0 or 1, with the proviso that at least one of m, n, and o is 1.

[0064] Generally, in the ligands of Formula 1, R1 is selected from C1-C9 alkyl, C4-C8 cycloalkyl, C5-C10 aryl, cyano, sulfonyl: -SO2-R10 (where R10 = C1-C5 alkyl, C5-C6 cycloalkyl, C5-C10 aryl), each of which is unsubstituted or substituted with one or more C1-C4 alkyl, C1-C4 alkoxy, C1-C4 perfluoroalkyl; and silyl: Si(RRR40), each of R20, R30, and R40 independently is C1-C6 alkyl, or C5-C10 aryl, each of which is unsubstituted or substituted with C1-C4 alkyl, or R1 is C5-C10 aryl, optionally substituted one or more times with C1-C5 alkyl, C1-C5 alkoxy, or C1-C5 perfluoroalkyl.

[0065] In certain embodiments, R1 represents C1-C9 alkyl, C4-C8 cycloalkyl, C5-C10 aryl, which is unsubstituted or substituted with C1-C5 alkyl, C1-C5 alkoxy, or C1-C5 perfluoroalkyl.

[0066] More specifically, R1 is selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-pentyl (amyl), 2-pentyl (sec-pentyl), 3-pentyl, 2-methylbutyl, 3-methylbutyl (iso-pentyl or iso-amyl), 3-methylbut-2-yl, 2-methylbut-2-yl, 2,2-dimethylpropyl (neopentyl), n-hexyl, trifluoromethyl, cyclobutyl, cyclopentyl, cyclohexyl, menthyl, phenyl, o-toluyl, naphthyl, o-methoxyphenyl, o-ethoxyphenyl, di-(o-methoxy)phenyl, p-trifluoromethylphenyl, trimethylsilyl, triisopropyl-silyl, tri-tert-butylsilyl, cyano, methylsulfonyl, toluenesulfonyl, and trifluoromethylsulfonyl.

[0067] Further, in the ligands of Formula 1, R2 is generally C1-C9 alkyl, C4-C8 cycloalkyl, adamantyl, C5-C10 aryl, which is unsubstituted or substituted with one or more C1-C5 alkyl, C1-C5 alkoxy, or C1-C5 perfluoroalkyl.

[0068] More specifically, R2 is selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-pentyl (amyl), 2-pentyl (sec-pentyl), 3-pentyl, 2-methylbutyl, 3-methylbutyl (isopentyl or iso-amyl), 3-methylbut-2-yl, 2-methylbut-2-yl, 2,2-dimethylpropyl (neopentyl), n-hexyl, trifluoromethyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, phenyl, o-, m-, or p-methylphenyl, naphthyl.

[0069] R3, R4, and R5 are, independently of one another, C1-C9 alkyl, C4-C8 cycloalkyl, adamantyl, 1-adamantyl, 2-adamantyl, or C5-C10 aryl, which are unsubstituted or substituted with C1-C5 alkyl, C1-C5 alkoxy, or C1-C5 perfluoroalkyl. Alternatively, at least two of R3, R4, and R5 are a C2-C10 alkyl bridge, a C2-C10 alkenyl bridge, or a C2-C10 alkyl ether bridge, which, together with the phosphorus atom, form a heterocyclyl ring.

[0070] That is, for example, R3 can be a methyl or cyclohexyl ring bonded directly to the phosphorus atom when m is 0 (zero), but R4 and R5 together can be a C2 alkenyl bridge or a C3 alkyl bridge, and n and o are 1, meaning that they can form a five-membered unsaturated ring consisting of P and two substituted nitrogen atoms both bonded to a C2 alkenyl bridge, or a six-membered saturated ring consisting of P and two substituted nitrogen atoms both bonded to a C3 alkyl bridge.

[0071] More specifically, R3, R4, and R5 are each independently C1-C5 alkyl, C4-C8 cycloalkyl, adamantyl, 1-adamantyl, 2-adamantyl, or C5-C6 aryl, which may be unsubstituted or substituted with C1-C5 alkyl, C1-C5 alkoxy, or C1-C5 perfluoroalkyl, or at least two of R3, R4, and R5 are a C2-C5 alkyl bridge, a C2-C5 alkenyl bridge, or a C2-C4 alkyl ether bridge, which, together with the phosphorus atom, form a heterocyclyl ring.

[0072] In another embodiment, at least two of R3, R4, and R5, taken together, are a C2-C8 alkyl bridge, or a C2-C8 alkyl ether bridge, optionally substituted with one or more C1-C5 alkyl or cycloalkyl groups, or the C2-C8 alkyl bridge or C2-C8 alkyl ether bridge is part of a fused C4-C8 cycloalkyl ring, which, together with the phosphorus atom, forms a heterocyclyl ring.

[0073] That is, for example, R3 can be a methyl or cyclohexyl ring bonded directly to the phosphorus atom when m is 0 (zero), but R4 and R5 together can be a 1,2-cyclohexyl bridge, where n and o are 1, forming a five-membered unsaturated ring consisting of P and two substituted nitrogen atoms, each bonded to positions 1 and 2 of the cyclohexyl ring, meaning that a C2 alkyl bridge is provided such that the heterocyclyl five-membered ring is fused to the cyclohexyl ring.

[0074] In another embodiment, R6, R7, and R8 are, independently of each other, C1-C9 alkyl, or C5-C10 aryl, which is unsubstituted or substituted with one or more C1-C5 alkyl, C1-C5 alkoxy, or C1-C5 perfluoroalkyl, or R6, R7, and R8, together with R3, R4, or R5 and the nitrogen atom to which they are attached, individually or collectively form a heterocyclyl ring.

[0075] In yet another embodiment, R3 and R6, and / or R4 and R7, and / or R5 and R8, taken together, are a C2-C8 alkyl bridge, or a C2-C8 alkyl ether bridge, optionally substituted with one or more C1-C5 groups, or may be part of a fused C4-C8 cycloalkyl ring, where the C2-C8 alkyl bridge, or the C2-C8 alkyl ether bridge, together with the nitrogen atom to which they are attached, form a heterocyclyl ring.

[0076] That is, in this embodiment, at least one of m, n, and o is 1, and at least one of R3, R4, or R7 is also connected to the nitrogen atom through the remaining R6, R7, and R8, each of which is bonded to the same nitrogen atom, to form an aliphatic ring with the nitrogen atom that may optionally contain one or more oxygen atoms as ring members.

[0077] In particular, R3 and R6 together may form, for example, an aziridine, pyrrolidine, or piperidine ring, or in the case of an alkyl ether bridge, may form, for example, an oxaziridine, oxazolidine, isoxazolidine, or morpholine ring. The same is possible with R4 and R7, R5 and R8, or R3 and R6, R4 and R7, and two or all of R5 and R8.

[0078] In a further 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(amyl), 2-pentyl(sec-pentyl), 3-pentyl, 2-methylbutyl, 3-methylbutyl(iso-pentyl or iso-amyl), 3-methylbut-2-yl, 2-methylbut-2-yl, 2,2-dimethylpropyl(neopentyl), n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, and mesityl.

[0079] In all of the preceding embodiments, at least one of m, n, and o must be 1. For all ligands in any of the preceding embodiments, at least two of m, n, and o can be 1.

[0080] In some embodiments, it may also be possible for ligands in which m, n, and o are all 1.

[0081] A further embodiment is a ligand comprising: R1 is C1-C9 alkyl or C5-C10 aryl (each of which is unsubstituted or substituted with C1-C4 alkyl), or sulfonyl: -SO2-R10 (R10 = C5-C10 aryl, which is unsubstituted or substituted with C1-C4 alkyl); R2 is C1-C9 alkyl, C4-C8 cycloalkyl, or adamantyl, and can be 1-adamantyl or 2-adamantyl; R3, R4, and R5 are, independently of one another, C1-C9 alkyl, C4-C8 cycloalkyl, adamantyl, or C5-C10 aryl; R6, R7, and R8 are C1-C9 alkyl or C5-C10 aryl, which are unsubstituted or substituted with one or more C1-C5 alkyls; and / or R3 and R6, and / or R4 and R7, and / or R5 and R8 together are a C2-C8 alkyl bridge, or a C2-C8 alkyl ether bridge, optionally wherein said C2-C8 alkyl bridge may be part or all of a fused C4-C8 cycloalkyl ring.

[0082] Yet a further embodiment is a ligand comprising: R1 is C1-C9 alkyl or C5-C10 aryl (each of which is unsubstituted or substituted with C1-C4 alkyl), or sulfonyl: -SO2-R10 (R10 = C5-C10 aryl, which is unsubstituted or substituted with C1-C4 alkyl); R2 is C1-C9 alkyl, C4-C8 cycloalkyl, or adamantyl (which may be 1-adamantyl or 2-adamantyl); at least two of m, n, and o are 1; at least two of R3, R4, or R5, taken together, are a C2-C8 alkyl bridge, or a C2-C8 alkyl ether bridge, which may be optionally substituted with one or more C1-C5 alkyl or cycloalkyl groups, or the C2-C8 alkyl bridge or C2-C8 alkyl ether bridge is part of a fused C4-C8 cycloalkyl ring, which, together with the phosphorus atom, may form a heterocyclyl ring; R6, R7, and / or R8 are C1-C6 alkyl or C5-C10 aryl, which may be unsubstituted or substituted with one or more C1-C5 alkyls; with the proviso that when 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, and may be 1-adamantyl or 2-adamantyl.

[0083] Another embodiment is a ligand comprising: R1 is C1-C9 alkyl or C5-C10 aryl (each of which is unsubstituted or substituted with C1-C4 alkyl), or sulfonyl: -SO2-R10 (R10 = C5-C10 aryl, which is unsubstituted or substituted with C1-C4 alkyl); R2 is C1-C9 alkyl, C4-C8 cycloalkyl, or adamantyl, and may be 1-adamantyl or 2-adamantyl; R3, R4, and R5 are, independently of one another, C1-C9 alkyl, C4-C8 cycloalkyl, adamantyl which may be 1-adamantyl or 2-adamantyl, or C5-C10 aryl; R6, R7, and R8 are C1-C9 alkyl or C5-C10 aryl, which are unsubstituted or substituted with one or more C1-C5 alkyls; and / or R3 and R6, and / or R4 and R7, and / or R5 and R8 together are a C2-C8 alkyl bridge, or a C2-C8 alkyl ether bridge, optionally wherein said C2-C8 alkyl bridge may be part or all of a fused C4-C8 cycloalkyl ring.

[0084] Yet another embodiment is a ligand comprising: R1 is C1-C9 alkyl or C5-C10 aryl, each of which is unsubstituted or substituted with one or more C1-C4 alkyl; R2 is C1-C9 alkyl, C4-C8 cycloalkyl, or adamantyl, and may be 1-adamantyl or 2-adamantyl; m is 0, n and o are 1, R3 is a C4-C8 cycloalkyl or adamantyl, which may be 1-adamantyl or 2-adamantyl; R4 and R5 are a C2-C8 alkyl bridge or a C2-C8 alkyl ether bridge that together form a heterocyclyl ring with the phosphorus atom, and the C2-C8 alkyl bridge or the C2-C8 alkyl ether bridge may optionally be substituted with one or more C1-C5 alkyl groups, or the C2-C8 alkyl bridge or the C2-C8 alkyl ether bridge may be part of a fully or partially fused C4-C8 cycloalkyl ring; R7 and R8 relate to ligands in which R7 and R8 are C1-C9 alkyl, or C5-C10 aryl, which are unsubstituted or substituted with one or more C1-C5 alkyls.

[0085] A further embodiment is a ligand comprising: R1 is C1-C9 alkyl or C5-C10 aryl, each of which is unsubstituted or substituted with one or more C1-C4 alkyl; R2 is C1-C9 alkyl, C4-C8 cycloalkyl, or adamantyl, and may be 1-adamantyl or 2-adamantyl; m, n, and o are 1; R3, R4, and R5 are, independently of one another, C1-C9 alkyl, C4-C8 cycloalkyl, or C5-C10 aryl, and R6, R7, and R8 are C1-C9 alkyl or C5-C10 aryl, which are unsubstituted or substituted with one or more C1-C5 alkyls.

[0086] In another embodiment, the ligand contains a substituent: R1 is C1-C9 alkyl or C5-C10 aryl, each of which is unsubstituted or substituted with one or more C1-C4 alkyl; R2 is C1-C9 alkyl, C4-C8 cycloalkyl, or adamantyl, and may be 1-adamantyl or 2-adamantyl; m, n, and o are 1; Each pair of R3 and R6, R4 and R7, and R5 and R8 taken together is a C2-C8 alkyl bridge or a C2-C8 alkyl ether bridge, and optionally the C2-C8 alkyl bridge may be part or all of a fused C4-C8 cycloalkyl ring.

[0087] Specifically, R1 is selected from methyl, isopropyl, phenyl, and o-tolyl.

[0088] Specifically, R2 is selected from methyl, isopropyl, tert-butyl, cyclohexyl, phenyl, and adamantyl, which can be 1-adamantyl, or 2-adamantyl.

[0089] Specifically, R3, R4, and R5 are selected from methyl, phenyl, and mesityl.

[0090] Specifically, one or more of R6, R7, and R8 is methyl, isopropyl, isopentyl, neopentyl, phenyl, or mesityl.

[0091] Specifically, in the ligands according to any 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 ring, or a morpholinyl ring.

[0092] A ligand according to any of the preceding items, 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, such that m, n, and o are all equal to 1.

[0093] The above-mentioned ligands have the ability to form metal complexes. Consequently, the present invention also relates to metal complexes comprising a metal and a ligand of formula 1, optionally comprising at least one organic ligand L, and / or at least one halogen X.

[0094] More specifically, the present invention also relates to a transition metal complex comprising a transition metal and a ligand of formula 1, optionally comprising at least one organic ligand L, and / or at least one halogen X.

[0095] Even more particularly, the transition metal is a noble metal.

[0096] 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, and in particular, selected from the group consisting of rhodium, iridium, palladium, and gold.

[0097] In the transition metal complexes of 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.

[0098] In the transition metal complexes of the ligands of formula 1, the halogen X is chlorine or bromine.

[0099] 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.

[0100] More specifically, the present invention also provides a method for carrying out a coupling reaction, the method comprising: providing a reaction mixture comprising at least a substrate, a coupling partner and a metal complex comprising a ligand as described above, in particular a ligand according to any one of items 1 to 26 above; - reacting said substrate with said coupling partner in the presence of a metal complex or a derivative thereof to form a coupling product.

[0101] In the method for carrying out the coupling reaction, the metal complex comprising the ligand is as described above, in particular a metal complex as defined in any one of the above items 27 to 31.

[0102] The substrate may be a substituted unsaturated or substituted aromatic compound, in particular a substituted aromatic compound which may be an aromatic or heteroaromatic compound.

[0103] The substrate may be substituted with, inter alia, a leaving group or an unsaturated aliphatic group, whereby it has been shown to be useful when the leaving group is selected from the group consisting of a halogen, particularly Cl, Br, or I (chlorine, bromine, iodine), triflate, tosylate, nosylate, and mesylate, and / or when the unsaturated aliphatic group is an alkene or alkyne, particularly selected from the group consisting of 2 to 12, especially 2 to 8, carbon atoms.

[0104] The coupling partner may comprise an organometallic compound, which may in particular be selected from the group consisting of organoboron, organolithium, organozinc, organolithium and Grignard compounds, and advantageously the organometallic compound comprises at least one aromatic group, or the organometallic compound comprises at least one unsaturated aliphatic group, or the organometallic compound comprises at least one saturated aliphatic group.

[0105] Specifically, in the method of performing a coupling reaction, the coupling reaction may 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 to alkynes and alkenes; (iv) catalytic coupling reactions, (v) catalytic Kumada, Murahashi, Negishi, or Suzuki coupling reactions, especially for the formation of biarylenes; (vi) catalytic cross-coupling reactions, in particular CN and CO coupling reactions, and / or (vii) catalytic Heck coupling reactions, particularly for the preparation of arylated olefins, and Sonogashira coupling reactions, particularly for the preparation of arylated and alkenylated alkynes; (viii) Catalytic α-arylation of carbonyl compounds and imines.

[0106] More specifically, the ligands and their transition metal complexes, especially their palladium complexes, are particularly useful for the catalytic α-arylation of carbonyl compounds and imines, especially carbonyl compounds, more particularly ketones. They have been found to be particularly useful for the arylation of acetone. For this purpose, ligands of formula 2 have been found to be particularly useful:

[0107] [ka]

[0108] wherein A is methyl or o-tolyl, B is cyclohexyl or isopropyl, and C is piperidyl or morpholyl, both of which are bonded to the P atom through their ring nitrogen atoms, such as compounds defined as in the following table:

[0109] [Table 1]

[0110] These ligands are used as transition metal complexes as defined above.

[0111] The present invention will be explained in more detail in the following examples. These are illustrative of the presentation of ligands, their preparation, and their metal complexes, their preparation, and their use in catalysis. The examples should not be understood as limiting the scope of protection of the present invention. [Example]

[0112] Example Synthesis and characterization of amine and phosphine precursors:

[0113] Synthesis of 10-P:

[0114] [ka]

[0115] N,N'-Dimethylethane-1,2-diamine (2.47 g, 3.02 mL, 27.2 mmol) and triethylamine (6.59 g, 9.15 mL, 64.8 mmol) were dissolved in Et2O (150 mL). CyPCl2 (4.80 g, 4.00 mL, 25.9 mmol) was added slowly at -94 °C to give a colorless suspension, which was allowed to warm to room temperature overnight. The solid was filtered and extracted with Et2O (3 × 20 mL). The solvent was removed in vacuo, and the oily residue was purified by Kugelrohr distillation (60 °C, 1.0 to 10-20 °C). 3 The product was obtained as a colorless oil.

[0116] Yield: (2.85 g, 14.2 mmol, 55%).

[0117] 1 H NMR (400 MHz, 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 (101 MHz, C6D6): δ = 54.8 (d, 2 J CP = 7.0 Hz, NCH2), 41.7 (d, 1 J CP = 21.2 Hz, Cy, C1), 40.7 (d, 2 J CP = 26.6 Hz, NCH3), 27.6 (d, 3 J CP = 17.4 Hz, Cy, C3), 27.1 - 26.9 (m, Cy, C2+4)ppm. 31 P{ 1H} NMR (162 MHz, 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 .

[0118] Synthesis of 11-P:

[0119] [ka]

[0120] N,N'-Diisopropylethylenediamine (7.98 g, 10.0 mL, 53.7 mmol) and triethylamine (16.4 g, 22.8 mL, 161 mmol) were dissolved in EtO (250 mL) and cooled to 0 °C. Phosphorus trichloride (8.11 g, 5.17 mL, 59.1 mmol) was added dropwise, and the colorless suspension was stirred at room temperature overnight. The solid was filtered and extracted with EtO (3 × 50 mL), and all volatiles were removed in vacuo to give a yellow oil. The compound was redissolved in EtO (150 mL) and cooled to 0 °C. CyMgCl (1.35 M in EtO, 39.8 mL, 53.7 mmol) was slowly added, and the suspension was allowed to warm to room temperature overnight. The solid was filtered, extracted with EtO (3 x 50 ml), and the solvent was 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 Kugelrohr distillation (100 °C, 1.0-10 ~3 The product was obtained as a colorless oil.

[0121] Yield: (7.77 g, 30.3 mmol, 57%).

[0122] 1H NMR (400 MHz, C6D6): δ = 3.20 - 3.00 (m, 4H, CH(CH3)2+ NC2H4N), 2.73 - 2.64 (m, 2H, NC2H4N), 1.96- 1.86 (m, H 2H ax. ), 1.86 to 1.79 (m, 2H, Cy, H2 ax. ), 1.69 – 1.62 (m, 1H, Cy, H4 ax. ), 1.43–1.32 (m, 1H, Cy, H1), 1.29 – 1.17 (m, 5H, Cy, H eq. ), 1.13 (d, 3 J HH = 17.4 Hz, 4 J HP = 6.5 Hz, 12H, CH(CH3)2)ppm. 13 C{ 1 H} NMR (101 MHz, C6D6): δ = 52.4 (d, 2 J CP = 23.0 Hz, CH(CH3)2), 50.1 (d, 2 J CP = 6.5 Hz, NC2H4N), 41.4 (d, 1 J CP = 14.5 Hz, Cy, C1), 28.1 (d, 3 J CP = 17.8 Hz, Cy, C3), 27.2 (d, 2 J CP = 11.4 Hz, Cy, C2), 27.2 (d, 4 J CP = 1.4 Hz, Cy, C4), 23.7 (d, 3 J CP = 14.0 Hz, CH(CH3)2), 23.4 (d, 3 J CP = 6.5 Hz, CH(CH3)2)ppm. 31 P{ 1H} NMR (162 MHz, 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 .

[0123] Synthesis of N,N'-diisopentylethane-1,2-diamine

[0124] [ka]

[0125] 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 small portions, after which the suspension was refluxed for 2 hours. Water (100 ml) was added, and the mixture was extracted with hexane (3 x 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%.

[0126] Yield (crude): (4.79 g, 18.0 mmol, 60%).

[0127] 1H NMR (400 MHz, 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 = 6.6 Hz, 12H, CH(CH3)2)ppm. 13 C{ 1 H} NMR (101 MHz, 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.

[0128] Synthesis of 12-Cl:

[0129] [ka]

[0130] N,N'-Diisopentylethylenediamine (15.5 g, 77.4 mmol) and triethylamine (19.7 g, 27.3 mL, 193 mmol) were dissolved in Et2O (250 mL) and cooled to 0 °C. Phosphorus trichloride (10.6 g, 6.76 mL, 77.4 mmol) was added dropwise to give a colorless suspension that turned yellow within 1 h. After allowing the suspension to warm to room temperature over 2 h, the suspension was filtered and the off-white solid was extracted with Et2O (3 × 50 mL). All volatiles from the combined orange filtrates were removed in vacuo. The oily brown residue was subjected to Kugelrohr distillation (100 °C, 1.0-10 ~3 The product was obtained as a colorless oil.

[0131] Yield: (5.74 g, 21.7 mmol, 28%).

[0132] 11H NMR (400 MHz, 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 = 6.5 Hz, 12H, CH3) ppm. 13 13C{1H} NMR (101 MHz, C6D6): δ = 50.1 (d, 1 H} NMR (101 MHz, C6D6): δ = 50.1 (d, 2 J CP = 10.5 Hz, NCH2CH2), 45.9 (d, 2 J CP = 16.0 Hz, NC2H4N), 37.9 (d, 3 J CP = 10.1 Hz, NCH2CH2), 26.1 (s, CH), 22.6 (d, 5 J CP = 27.4 Hz, CH3) ppm. 31 31P{1H} NMR (162 MHz, C6D6): δ = 163.0 ppm. IR (ATR): 2954 (s), 2867 (m), 1466 (m), 1366 (m), 1145 (s), 1121 (s), 1061 (s), 699 (m), 413 (s) cm 1 H} NMR (162 MHz, C6D6): δ = 163.0 ppm. IR (ATR): 2954 (s), 2867 (m), 1466 (m), 1366 (m), 1145 (s), 1121 (s), 1061 (s), 699 (m), 413 (s) cm -1 .

[0133] Synthesis of 12 - P:

[0134]

Chemical Structure

[0135] Chlorophosphine 12-Cl (4.58 g, 17.3 mmol) was dissolved in EtO (100 ml) and cooled to 0 °C. CyMgCl (1.35 M in EtO, 12.8 ml, 17.3 mmol) was slowly added and the resulting suspension was allowed to warm to room temperature over 2 h. The solid was filtered, extracted with EtO (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 and extracted with pentane (3 × 30 ml). The solvent of the grey filtrate was evaporated in vacuo and the residue was purified by Kugelrohr distillation (120 °C, 1.0·10 -3 The product was obtained as a colorless oil.

[0136] Yield: (3.80 g, 12.1 mmol, 70%).

[0137] 1 H NMR (400 MHz, 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 (101 MHz, C6D6): δ = 53.1 (d, 2 J CP = 25.5 Hz, NCH2CH2), 52.7 (d, 2 J CP = 6.6 Hz, NC2H4N), 41.5 (d, 1 J CP = 16.8 Hz, Cy, C1), 40.6 (d, 3 J CP= 9.7 Hz, NCH2CH2),), 27.9 (d, 4 J CP = 17.6 Hz, Cy, C3), 27.1 - 27.0 (m, Cy, C2+4), 26.1 (s, CH), 22.9 (d, 5 J CP = 19.1 Hz, CH3)ppm. 31 P{ 1 H} NMR (162 MHz, C6D6): δ = 128.7ppm. IR (ATR): 2952 (m), 2919 (s), 2848 (m), 1447 (w), 1366 (w), 1151 (s), 1119 (w)cm -1 .

[0138] Synthesis of 13-Cl:

[0139] [ka]

[0140] N,N'-Dineopentylethylenediamine (8.23 g, 41.1 mmol) and triethylamine (12.5 g, 17.4 mL, 123 mmol) were dissolved in EtO (300 mL) and cooled to 0 °C. Phosphorus trichloride (6.21 g, 3.95 mL, 45.2 mmol) was added dropwise to give a colorless suspension that turned yellow within 1 h. After allowing the suspension to warm to room temperature over 2 h, the suspension was filtered and the off-white solid was extracted with EtO (3 × 50 mL). The solvent of the combined orange filtrate was removed in vacuo. The oily brown residue was purified by Kugelrohr sublimation (100 °C, 1.0·10 -3 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 a saturated benzene solution.

[0141] Yield: (10.1 g, 38.1 mmol, 93%).

[0142] 1H NMR (400 MHz, C6D6): δ = 3.10 - 2.98 (m, 6H, NC2H4N+CH2), 2.37 (dd, 3 J HH = 14.4, 8.6 Hz, 2H, NC2H4N), 0.81 (s, 18H, CH3)ppm. 13 C{ 1 H} NMR (101 MHz, C6D6): δ = 59.9 (d, 2 J CP = 14.3 Hz, NC2H4N), 54.2 (d, 2 J CP = 10.1 Hz, CH2), 33.0 (d, 3 J CP = 6.6 Hz, C(CH3)3), 28.0 (d, 4 J CP = 1.8 Hz, CH3)ppm. 31 P{ 1 H} NMR (162 MHz, 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, measured values: C 54.02, H 10.27, N 10.62.

[0143] Synthesis of 13-P:

[0144]

change

[0145] Chlorophosphine 13-Cl (8.00 g, 30.2 mmol) and triethylamine (5.40 g, 7.50 mL, 53.1 mmol) were dissolved in EtO (200 mL) and cooled to 0 °C. CyMgCl (1.35 M in EtO, 22.4 mL, 53.1 mmol) was slowly added and the resulting suspension was allowed to warm to room temperature over 2 h. The solid was filtered and extracted with EtO (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 and extracted with pentane (3 × 30 mL). The solvent of the gray filtrate was evaporated in vacuo, and the residue was purified by Kugelrohr distillation (120 °C, 1.0 × 10 -3 The product was purified by filtration (300 rpm, 100 rpm, 100 mbar) and crystallized overnight as a colorless solid.

[0146] Yield: (7.38 g, 23.6 mmol, 78%).

[0147] 1 H NMR (400 MHz, C6D6): δ = 3.18 - 3.11 (m, 2H, NC2H4N), 3.06 (t, 3 J HP = 13.7 Hz, 4 J HH = 0.9 Hz, 2H, NCH2), 2.69 - 2.58 (m, 2H, NC2H4N), 2.38 (dd, 3 J HP = 13.5 Hz, 4 J HH = 5.1 Hz, 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 (101 MHz, C6D6): δ = 70.7 (d, 2 J CP= 26.8 Hz, NCH2), 57.0 (d, 2 J CP = 6.7 Hz, NC2H4N), 41.9 (d, 1 J CP = 13.3 Hz, Cy, C1), 34.4 (d, 3 J CP = 7.6 Hz, C(CH3)3), 28.5 (d, 3 J CP = 17.0 Hz, Cy, C3), 28.3 (s, CH3), 27.2 (d, 2 J CP = 11.1 Hz, Cy, C2), 26.9 (d, 4 J CP = 1.0 Hz, Cy, C4)ppm. 31 P{ 1 H} NMR (162 MHz, 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 values: C 69.19, H 11.93, N 8.96, measured values: C 69.48, H 12.00, N 9.08.

[0148] Synthesis of 14-P:

[0149]

change

[0150] 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. CyPCl (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 EtO (3 × 5 mL). The crude product was dissolved in hot EtO (100 mL), filtered, and slowly cooled to -30 °C. Colorless crystals formed, which were filtered and washed with cold EtO (3 × 10 mL). The product was 31 P{ 1 It was obtained as colorless crystals with a purity of about 95% according to H}NMR spectroscopy and was used without further purification. Colorless crystals suitable for single crystal X-ray diffraction experiments were obtained by recrystallization from hot EtO.

[0151] Yield: (3.89 g, 9.52 mmol, 37%).

[0152] 1 H NMR (400 MHz, C6D6): δ = 6.84 (s, 4H, CH, Mes meta ), 3.54 - 3.48 (m, 2H, NCH2), 2.90 - 2.84 (m, 2H, NCH2), 2.72 - 2.27 (m, 12H, CH3, Mes ortho ), 2.17 (s, 6H, CH3, Mes para ), 1.82 - 1.69 (m, 1H, Cy, H1), 1.60 - 1.43 (m, 5H, Cy, H2+H4 eq. ), 1.25 - 1.11 (m, 2H, Cy, H3 eq. ), 1.03 - 0.87 (m, 3H, Cy, H3 ax. +H4 ax. ) ppm. 13 C{ 1 H} NMR (101 MHz, C6D6): δ = 141.8 (d, 2 JCP = 14.4 Hz, Mes ipso ), 136.1 (s, Mes ortho ), 134.2 (d, J= 1.7 Hz, Mes para ), 130.2 (s, Mes meta ), 52.9 (d, 2 J CP = 5.9 Hz, NCH2), 46.7 (d, 1 J CP = 37.4 Hz, Cy, C1), 27.4 - 26.4 (m, Cy, C2-4), 21.1 - 19.6 (m, CH3, Mes ortho,para ) ppm. 31 P{ 1 H} NMR (162 MHz, C6D6): δ = 106.1ppm.

[0153] Synthesis of 15-P:

[0154] [ka]

[0155] (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 give 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 Kugelrohr distillation (105 °C, 1.0 10 -3 The product was obtained as a colorless oil.

[0156] Yield: (3.71 g, 14.6 mmol, 75%).

[0157] 1H NMR (400 MHz, C6D6): δ = 2.76 - 2.69 (m, 1H, Cy(NCH3)2, H1), 2.64 (d, 3 J HP = 14.9 Hz, 3H, NCH3), 2.51 (d, 3 J HP = 15.0 Hz, 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 (101 MHz, C6D6): δ = 70.0 (d, 2 J CP = 3.6 Hz, Cy(NCH3)2, C1), 67.0 (d, 2 J CP = 7.3 Hz, Cy(NCH3)2, C1), 41.1 (d, 1 J CP = 27.6 Hz, Cy, C1), 39.2 (d, 2 J CP = 33.4 Hz, NCH3), 33.9 (d, 2 J CP = 19.0Hz, NCH3), 31.2 (s, Cy(NCH3)2, C2), 29.1 (d, 3 J CP = 2.0 Hz, Cy(NCH3)2, C2), 28.6 (d, 3 J CP = 21.3 Hz, Cy, C3), 27.2 - 27.0 (m, Cy, C2+4), 26.9 (d, 3 J CP = 11.6 Hz, Cy, C3), 25.0 (s, Cy(NCH3)2, C3), 24.7 (s, Cy(NCH3)2, C3)ppm. 31 P{ 1H} NMR (162 MHz, 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 .

[0158] Synthesis of 16-P:

[0159] [ka]

[0160] Phosphorus trichloride (2.70 g, 1.75 mL, 20.0 mmol) was dissolved in EtO (150 mL) and cooled to 0 °C. Morpholine (13.1 g, 13.2 mL, 150 mmol) was slowly added, initiating the precipitation of a white solid. The suspension was stirred at room temperature for 1 h, and the solid was filtered and extracted with toluene (3 × 100 mL). All volatiles were removed in vacuo to give the product as a colorless solid.

[0161] Yield: (5.10 g, 17.6 mmol, 88%).

[0162] Synthesis of 17-P:

[0163] [ka]

[0164] N-Methylaniline (17.2 g, 17.5 mL, 160 mmol) and triethylamine (18.6 g, 25.8 mL, 183 mmol) were dissolved in toluene (200 mL) at 0°C. Phosphorus trichloride (6.28 g, 4.00 mL, 45.7 mmol) was slowly added, and the resulting suspension was allowed to warm to room temperature overnight. The solid was filtered and extracted with hot toluene (3 x 200 mL). The solvent was removed in vacuo to give an orange slimy residue, which was washed with EtO (3 x 50 mL). The product was obtained as an off-white solid. Colorless crystals suitable for single-crystal X-ray diffraction experiments were grown by slow evaporation of a saturated benzene solution.

[0165] Yield: (5.78 g, 16.53 mmol, 36%).

[0166] 1 H NMR (400 MHz, CD2Cl2): δ = 7.29 - 7.21 (m, 6H, Ph meta ), 7.07 - 7.01 (m, 6H, Ph ortho ), 6.92 (t, 3 J HH = 7.3 Hz, 3H, Ph para ), 3.02 (d, 3 J HP = 2.6 Hz, 9H, NCH3)ppm. 13 C{ 1 H} NMR (101 MHz, CD2Cl2): δ = 148.6 (d, 2 J CP = 24.2 Hz, Ph ipso ), 129.5 (d, 4 J CP = 1.8 Hz, Ph meta ), 120.7 (d, 5 J CP = 1.3 Hz, Ph para ), 117.1 (d, 3 J CP = 16.8 Hz, Ph ortho ), 33.4 (d, 2 J CP= 5.0 Hz, NCH3)ppm. 31 P{ 1 H} NMR (162 MHz, 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℃.

[0167] Synthesis and characterization of phosphonium salts:

[0168] Synthesis of 1·H2:

[0169] [ka]

[0170] 9 g of tripiperidinylphosphine (31.8 mmol, 1 equiv.) was dissolved in 40 ml of THF and slowly added to a solution of 7.6 ml (63.6 mmol, 2 equiv.) of benzyl bromide in 40 ml of THF at 0 °C. This was stirred at room temperature for 1 h, resulting in the precipitation of a beige solid. The suspension was filtered, and the residue was dissolved in 4 ml of DCM and hot filtered. The solution was covered with 10 ml of pentane. After 1 day, a white solid precipitated. The solution was filtered, and the solid was washed with 2 × 20 ml of pentane. 1·H2 was obtained as a colorless solid (12.1 g, 27.56 mmol, 86%).

[0171] 1 H-NMR (400 MHz, Chloroform-d): δ = 1.52 - 1.73 (m, 18H, Pip CH2H 2+3 ), 3.12 (q, 3 J = 5.9 Hz, 12H, Pip CH2H3), 4.39 (d, 2 J HP= 15.7 Hz, 2H, PCH2Ph), 7.23 - 7.38 (m, 3H, Ph para + meta CH), 7.43 - 7.51 (m, 2H, Ph ortho CH). 13 C-NMR (101 MHz, Chloroform-d): δ = 23.8 (d, 4 J CP = 1.2 Hz, Pip CH2C3), 25.8 (d, 3 J CP =5.1Hz, Pip CH2C2), 30.2 (d, 1 J CP = 100.7 Hz, PCH2Ph), 46.9 (s, Pip CH2C1), 128.1 (d, 2 J = 3.6 Hz, Ph para CH), 129.0 (s, Ph ypso C), 129.0 (d, 4 J CP = 3.2 Hz, Ph meta CH), 130.8 (d, 3 J CP = 6.1 Hz, Ph ortho 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 value: C: 58.15, H: 8.21, N: 9.25 Determined value: C: 57.95, H: 8.15, N: 9.53. Melting point: 209.9℃.

[0172] 2·H2 synthesis

[0173]

change

[0174] 4.5 g of tripiperidinylphosphine (15.9 mmol, 1 equiv.) was dissolved in 80 ml of toluene. 1.53 ml of iodoethane (19.1 mmol, 1.2 equiv.) was slowly added, and the solution was stirred overnight at room temperature. A colorless solid precipitated, which was then filtered, washed with 3 × 10 ml of pentane, and dried in vacuo. 2·H2 was obtained as a colorless solid (6.11 g, 13.91 mmol, 88%).

[0175] 1 H NMR (400 MHz, CDCl3): δ = 3.07 (q, J HH = 6.1 Hz, 12H, Pip Pos. 1 CH2), 2.61 (dq, J = 13.4, 7.6 Hz, 2H, P-CH2-CH3), 1.68 - 1.46 (m, 18H, Pip Pos. 2 + Pos. 3 CH2), 1.25 - 1.09 (m, 3H, CH3). 13 C NMR (101 MHz, CDCl3): δ = 46.3 (d, 2 J CP = 1.4 Hz, Pip Pos. 1 CH2), 25.9 (d, 3 J CP = 4.8 Hz, Pip Pos. 2 CH2), 23.7 (d, 4 J CP = 1.1Hz, Pip Pos. 3 CH2), 18.0 (d, 1 J CP = 105.3 Hz, P-CH2-CH3), 6.6 (d, 3 J CP = 5.4 Hz, CH3). 31 P NMR (162 MHz, CDCl3): δ = 54.5 (s).

[0176] Synthesis of 3·H2:

[0177] [ka]

[0178] 3.08 ml of cyclohexyldichlorophosphine (20 mmol, 1 equivalent) and 7 ml of triethylamine (50 mmol, 2.5 equivalents) were dissolved in 30 ml of diethyl ether and cooled to 0° C. A solution of 2.22 ml of N,N-dimethylethane-1,2-diamine (20 mmol, 1 equivalent) in 50 ml of diethyl ether was prepared and added slowly via an addition funnel at 0° C. over 1 hour. A colorless solid precipitated during the addition. The mixture was stirred overnight at room temperature. The solid was filtered, and 3.6 ml of benzyl bromide (30 mmol, 1.5 equivalents) was added to the solution. Stirring was continued overnight, during which time a colorless solid precipitated, which was then filtered, washed with 3×10 ml of THF, and dried in vacuo. 3·H2 was obtained as a colorless solid (5.4 g, 14.54 mmol, 73%) and used without further purification.

[0179] Synthesis of 4·H2:

[0180] [ka]

[0181] 4.5 ml of cyclohexyldichlorophosphine (29.2 mmol, 1 equivalent) and 12.4 ml of triethylamine (87.6 mmol, 3 equivalents) were dissolved in 50 ml of diethyl ether and cooled to 0° C. A solution of 3.24 ml of N,N-dimethylethane-1,2-diamine (29.2 mmol, 1 equivalent) in 70 ml of diethyl ether was prepared and added slowly via an addition funnel at 0° C. over 1 hour. A colorless solid precipitated during the addition. The mixture was stirred overnight at room temperature. The solid was filtered, and 2.34 ml of iodoethane (29.2 mmol, 1 equivalent) was added to the solution. The mixture was stirred overnight, during which time a colorless solid precipitated, which was then filtered, washed with 3×10 ml of THF, and dried in vacuo. 4·H2 was obtained as a colorless solid (6.2 g, 17.29 mmol, 60%).

[0182] 1H NMR (400 MHz, CD2Cl2): δ = 3.39 (d, 3 J HP = 7.4 Hz, 4H, MeN(CH2)2NMe), 2.97 - 2.91 (m (overlap), 1H, Cy Pos. 1 CH), 2.89 (d, 3 J HP = 9.6 Hz, 6H, NCHH3), 2.67 ( p, 2 J HP = 7.7 Hz, 2H, P-CH2-CH3), 1.93 - 1.70 (m, 5H, Cy Pos. 2+3+4 CH2), 1.49 - 1.18 (m, 5H, Cy Pos. 2+3+4, CH2), 1.10, CH (m)., m 13C NMR (101 MHz, CD2Cl2): δ = 51.1 (d, 2 J CP = 5.0 Hz, MeN(CH2)2NMe), 37.0 (d, 1 J CP = 63.3 Hz, Cy Pos. 1 CH), 33.0 (d, 2 J CP = 6.2 Hz, NCH3), 25.7 (d, 2 J CP = 14.5 Hz, Cy Pos. 2 CH2), 25.5 (d, 4 J CP = 1.8 Hz, Cy Pos. 4 CH2), 25.2 (d, 3 J CP = 3.6 Hz, Cy Pos. 3 CH2), 16.3 (d, 1 J CP = 59.1 Hz, P-CH2-CH3), 4.7 (d, 2 J CP = 7.0 Hz, P-CH2-CH3). 31 P NMR (162 MHz, 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. Found: C: 40.37, H: 7.56, N: 7.95. Melting point: 191.6°C (decomposition).

[0183] Synthesis of 5·H2:

[0184] [ka]

[0185] 5 g of tripiperidinephosphine (17.6 mmol, 1 equiv.) was dissolved in 80 ml of toluene. 2.44 ml of 1-iodo-2-methylpropane (21.1 mmol, 1.2 equiv.) was slowly added, and the solution was stirred under reflux overnight. A beige solid precipitated, which was then filtered, washed with 3 × 10 ml of pentane, and dried in vacuo. 5·H2 was obtained as a crystalline off-white solid (7.35 g, 15.73 mmol, 89%).

[0186] 1 H NMR (400 MHz, CD2Cl2): δ = 3.10 (q, J HH = 5.7 Hz, 12H, Pip Pos. 1 CH2), 2.37 (dd, 2 J HP = 13.8, J HH = 6.2 Hz, 2H, P-CH2-iPr), 2.02 (tp, 3 J HP =13.1 Hz, J HH= 6.5 Hz, 1H, iPr CH, 1.66 (m, 6H, Pip Pos. 2 CH2), 1.60 (q (br), J HH = 5.4 Hz, 12H, Pip Pos 3 CH2), 1.14 (d, J HH = 6.7 Hz, 6H, iPr CH3). 13 C NMR (101 MHz, CD2Cl2): δ = 46.8 (d, 2 J CP = 1.1 Hz, Pip Pos. 1 CH2), 31.7 (d, 1 J CP = 100.6 Hz, P-CH2-iPr), 26.0 (d, 2 J CP = 5.1 Hz, Pip Pos. 2 CH2), 24.6 (d, 3 J CP = 9.8 Hz, iPr CH3), 24.0 (d, 4 J CP = 1.2 Hz, Pip Pos. 3 CH2), 23.7 (d, 2 J CP = 3.4 Hz, iPr CH). 31 P NMR (162 MHz, CD2Cl2): δ = 52.5 (s). IR (ATR) [cm -1 ]: 3851 (w), 2929 (w), 2848 (w), 1451 (w), 1377 (w), 1332 (w), 1284 (w), 1201 (w), 1155 (w), 1103 (w), 1073 (s), 1024 (w), 940 (s), 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. Found: C: 48.82, H: 8.49, N: 8.74. Melting Point: 195.5°C.

[0187] Synthesis of 7·H2:

[0188] [ka]

[0189] 3.5 g of tripiperidinephosphine (12.4 mmol, 1 equiv.) was dissolved in 50 ml of THF. 2.42 ml of 2-methylbenzyl chloride (18.6 mmol, 1.5 equiv.) was slowly added, and the solution was stirred under reflux for 2 days. A beige solid precipitated, which was then filtered, washed with 3 × 10 ml of pentane, and dried in vacuo. 7·H2 was obtained as an off-white solid (3.72 g, 8.77 mmol, 71%).

[0190] 1 H NMR (400 MHz, CD2Cl2): δ = 7.44 - 7.07 (m, 4H, CH oTol), 3.87 (d, 2 J HP = 15.7 Hz, 2H, PCH2), 3.05 (q, 3 J = 5.8 Hz, 12H, CH2Pip Pos. 1), 2.45 (d, 4 J = 1.4 Hz, 3H, CH3oTol), 1.69 - 1.62 (m, 6H, CH2Pip Pos. 3), 1.61 - 1.53 (m, 12H, CH3Pip Pos. 2). 13 C NMR (101 MHz, CD2Cl2): δ = 137.4 (d, 2 J CP = 7.7 Hz, C oTol Pos. 1), 131.8 (d, 3 J CP = 2.6 Hz, CH oTol Pos. 6), 130.5 (d, J = 5.1 Hz, CH oTol Pos. 4), 128.9 (d, J = 3.5 Hz, CH oTol Pos. 3), 127.8 (d, 3 J CP= 7.7 Hz, C oTol Pos. 2), 127.1 (d, J = 3.3 Hz, CH oTol Pos. 5), 47.3 (s, CH2Pip Pos. 1), 27.6 (d, 1 J CP = 108.1 Hz, PCH2), 26.1 (d, 3 J CP = 5.1 Hz, CH 2, Pip Pos. 2), 24.1 (d, 3 J CP = 1.2 Hz, CH2Pip Pos. 3), 21.1 (s, CH3oTol). 31 P NMR (162 MHz, 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), 1071 (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℃.

[0191] Synthesis of 10·H2:

[0192] [ka]

[0193] 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 overnight at room temperature. The colorless solid was filtered 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.

[0194] Yield: (4.58 g, 10.6 mmol, 99%).

[0195] 1 1H NMR (400 MHz, CDCl3): δ = 7.23 - 7.18 (m, 1H, oTol ortho ), 7.15 - 7.05 (m, 3H, oTol meta+para ), 4.15 (d, 2 J HP = 10.9 Hz, 2H, CH2oTol), 3.58 - 3.45 (m, 1H, Cy, H1), 3.2 - 3.1 (m, 2H, NC2H4N), 2.9 (d, 3 J HP = 9.5 Hz, 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 13C{ 1 1H} NMR (101 MHz, CDCl3): δ = 137.2 (d, 2 J CP = 5.8 Hz, oTol ipso ), 131.1 (d, 4 J CP = 3.1 Hz, oTol meta ), 130.6 (d, 3 J CP = 5.1 Hz, oTol ortho ), 128.1 (d, 4 J CP = 3.5 Hz, oTol meta’ ), 126.4 (d, 3 J CP = 10.6 Hz, oTol ortho’ ), 126.3 (d, 5 J CP = 3.3 Hz, oTol para), 50.6 (d, 2 J CP = 4.6 Hz, NC2H4N), 36.8 (d, 1 J CP = 59.1 Hz, Cy, C1), 33.5 (d, 2 J CP = 6.4 Hz, NCH3), 29.0 (d, 1 J CP = 54.6 Hz, CH2oTol), 25.7 - 25.2 (m, Cy, C2-4), 20.7 (d, 4 J CP =1.4Hz, CH3)ppm. 31 P{ 1 H} NMR (162 MHz, CDCl3): δ = 78.2ppm. IR (ATR): 2851 (w), 1446 (m), 1250 (m), 1223 (m), 1203 (m), 1160 (m), 1144 (m), 1037 (s), 948 (s), 861 (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.

[0196] Synthesis of 11·H2:

[0197] [ka]

[0198] 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, precipitation of a colorless solid began, and the mixture was stirred at room temperature for 72 h. The colorless solid was filtered and washed with toluene (3 × 20 mL) and pentane (3 × 20 mL). The phosphonium salt 11·H2 was obtained as a colorless solid. Colorless crystals suitable for single-crystal X-ray diffraction experiments were obtained by slow vapor diffusion of pentane into a saturated THF solution of the compound.

[0199] Yield: (12.7 g, 25.9 mmol, 95%).

[0200] 1 H 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 - 2.07 (m, 2H, Cy, H3), 1.90 - 1.74 (m, 3H, Cy, H3+4), 1.70 - 1.55 (m, 2H, Cy, H2), 1.42-1.30 (m, 2H, Cy, H2), 1.23 (d, 3 J HH = 6.5 Hz, 7H, CH(CH3)2+ Cy, H4), 0.85 (d, 3 J HH = 6.5 Hz, 6H, CH(CH3)2)ppm. 13 C{ 1 H} NMR (101 MHz, CDCl3): δ =137.3 (d, 2 J CP = 7.6 Hz, oTol ipso ), 131.5 (d, 4 J CP = 2.1 Hz, oTolmeta ), 128.6 (d, 3 J CP = 5.7 Hz, oTol ortho ), 128.1 (d, 4 J CP = 2.6 Hz, oTol meta’ ), 127.6 (d, 3 J CP = 9.1 Hz, oTol ortho’ ), 126.5 (d, 5 J CP = 2.5 Hz, oTol para ), 45.8 (d, 2 J CP = 6.5 Hz, CH(CH3)2), 40.8 (d, 2 J CP = 6.4 Hz, NC2H4N), 39.1 (d, 1 J CP = 61.6 Hz, Cy, C1), 27.2 (d, 1 J CP = 56.9 Hz, CH2ºTol), 25.8 (d, 3 J CP = 3.6 Hz, Cy, C3), 25.7 - 25.6 (m, Cy, C2), 25.5 (s, Cy, C4) 21.6 (d, 3 J CP = 2.7 Hz, CH(CH3)2), 21.2 (s, CH3), 20.6 (d, 3 J CP =3.3Hz, CH(CH3)2)ppm. 31 P{ 1 H} NMR (162 MHz, 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), 556 (m), 556 (m). (m), 470 (s)cm -1 . Temperature:160°C 22 H 38Elemental analysis of IN2P: Calculated: C 54.10, H 7.84, N 5.74; Found: C 54.35, H 7.78, N 5.67.

[0201] Synthesis of 12·H2:

[0202] [ka]

[0203] A solution of 2-methylbenzyl iodide (3.27 g, 14.1 mmol) in EtO (30 mL) was transferred to a solution of phosphine 12-P in EtO (100 mL). After a few minutes, precipitation of a colorless solid began, and the suspension was stirred at room temperature overnight. The colorless solid was filtered and washed with EtO (3 × 50 mL). The crude product was extracted with hot THF (30 mL), and the filtrate was slowly cooled to −30 °C. Colorless crystals formed, which were filtered and washed with cold THF (3 × 5 mL). The phosphonium salt 12·H was obtained as a colorless solid after drying in vacuo at 140 °C for 10 h. Colorless crystals suitable for single-crystal X-ray diffraction experiments were obtained by recrystallization from hot toluene.

[0204] Yield: (3.86 g, 7.08 mmol, 50%).

[0205] 1 H NMR (400 MHz, CDCl3): δ = 7.24 - 7.14 (m, 4H, oTol), 4.19 (d, 2 J HP= 10.9 Hz, 2H, CH2OTol), 3.67 - 3.57 (m, 1H, Cy, H1), 3.36 - 3.22 (m, 4H, NC2H4N+NCH2CH2), 3.03 - 2.97 (m, 4H, NC2H4N'+NCH2CH2'), 2.43 (s, 3H, CH3), 2.17 - 2.08 (m, 2H, Cy), 1.92 - 1.81 (m, 3H, Cy), 1.71 - 1.58 (m, 4H, CH(CH3)2+Cy), 1.45 - 1.31 (m, 7H, NCH2CH2+Cy), 0.92 (dd, 3 J HH = 6.6, 3.0 Hz, 12H, CH(CH3)2)ppm. 13 C{ 1 H} NMR (101 MHz, CDCl3): δ = 137.2 (d, 2 J CP = 6.3 Hz, oTol ipso ), 131.4 (d, 4 J CP = 2.8 Hz, oTol meta ), 129.9 (d, 3 J CP = 5.1 Hz, oTol ortho ), 128.2 (d, 4 J CP = 3.3 Hz, oTol meta’ ), 127.0 (d, 3 J CP = 9.9 Hz, oTol ortho’ ), 126.5 (d, 5 J CP = 3.0 Hz, oTol para ), 47.4 (d, 2 J CP = 5.1 Hz, NC2H4N), 44.6 (d, 2 J CP = 5.1 Hz, NCH2CH2), 37.6 (d, 1 J CP = 60.5 Hz, Cy, C1), 37.4 (d, 3 J CP= 4.4 Hz, NCH2CH2), 28.6 (d, 1 J CP = 54.0 Hz, CH2oTol), 26.1 (s, CH(CH3)2), 25.7 - 25.4 (m, Cy, C2+3+4), 22.7 (d, 5 J CP = 3.6 Hz, CH(CH3)2), 21.2 (s, CH3)ppm. 31 P{ 1 H} NMR (162 MHz, 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.

[0206] Synthesis of 13·H2:

[0207] [ka]

[0208] 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 EtO (3 × 10 mL). The phosphonium salt 13·H was obtained as a colorless solid. Colorless crystals suitable for single-crystal X-ray diffraction experiments were obtained from the combined washing solutions.

[0209] Yield: (9.24 g, 20.7 mmol, 95%).

[0210] 1 H NMR (400 MHz, CDCl3): δ = 3.55 − 3.41 (m, 4H, NC2H4N), 3.12 − 2.74 (m, 7H, NCH2+Cy, H1+CH2CH3), 2.08 − 1.97, Cy.8, H 2H (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.1894) (m, 0,9). 13 C{ 1 H} NMR (101 MHz, CDCl3): δ = 58.8 (d, 2 J CP = 3.0 Hz, NCH2), 52.1 (d, 2 J CP = 4.7 Hz, NC2H4N), 37.2 (d, 1 J CP = 62.3 Hz, Cy, C1), 33.8 (d, 3 J CP = 5.3 Hz, 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 = 1.8 Hz, Cy, C4), 24.9 (d, 2 J CP = 3.6 Hz, Cy, C2), 17.9 (d, 1 J CP =58.2Hz, CH2CH3), 4.7 (d, 2 J CP = 7.4 Hz, CH2CH3)ppm. 31 P{ 1H} NMR (162 MHz, 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.

[0211] Synthesis of 14·H2:

[0212] [ka]

[0213] 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 EtO (20 mL) and a colorless suspension was obtained when the mixture was allowed to warm to room temperature. The colorless solid was filtered and washed with EtO (3 × 10 mL). The crude phosphonium salt 14·H 31 P{ 1 It was obtained as a colorless solid with 90% purity according to {H}NMR spectroscopy.

[0214] Yield: (300 mg, 0.478 mmol, 37%).

[0215] 1 H NMR (400 MHz, CDCl3): δ = 6.94 (s, 4H, Mes meta ), 4.05 - 3.86 (m, 4H, NCH2), 2.65 - 2.52 (m, 2H, CH2CH3), 2.47 (s, 6H, Mes para , CH3), 2.44 (s, 6H, Mes ortho, CH3), 2.37 to 2.29 (m, 1H, Cy, H1), 2.27 (s, 6H, Mes ortho’ , 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 (101 MHz, CDCl3): δ = 139.3 (d, 5 J CP = 1.4 Hz, We para ), 137.5 (d, 3 J CP = 1.8 Hz, We ortho ), 137.4 (d, 3 J CP = 2f.1 Hz, We ortho’ ), 132.7 (d, 2 J CP = 4.9 Hz, We ipso ), 131.0 (s, We meta ), 130.6 (s, We meta’ ), 52.1 (d, 2 J CP = 8.4 Hz, NCH2), 41.9 (d, 1 J CP = 60.0 Hz, Cy, C1), 26.5 (d, 3 J CP = 14.0 Hz, Cy, C3), 26.2 (d, 2 J CP = 2.9 Hz, Cy, C2), 25.5 (d, 4 J CP = 1.8 Hz, Cy, C4), 21.7 (d, 1 J CP = 61.2 Hz, CH2CH3), 21.0 (s, Month para , CH3), 20.1(s, We ortho , CH3), 19.4 (s, We ortho’ , CH3), 7.6 (d, 2 JCP = 4.7 Hz, CH2CH3)ppm. 31 P{ 1 H} NMR (162 MHz, CDCl3): δ = 66.8ppm.

[0216] Synthesis of 15·H2:

[0217] [ka]

[0218] 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 overnight at room temperature. The colorless solid was filtered and washed with THF (3 × 20 mL). The phosphonium salt 15·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 chloroform solution of the compound.

[0219] Yield: (6.33 g, 13.0 mmol, 99%). 1 H NMR (400 MHz, CDCl3): δ = 7.36 - 7.31 (m, 1H, oTol ortho ), 7.21 - 7.10 (m, 3H, oTol meta+para ), 4.39- 4.21 (m, 2H, Cy(NCH3)2, H1), 3.68 - 3.58 (m, 1H, Cy, H1), 2.92 (d, 3 J HP = 10.9 Hz, 3H, NCH3), 2.85 (d, 3 J HP= 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. 13 C{ 1 H} NMR (101 MHz, CDCl3): δ = 137.6 (d, 2 J CP = 5.5 Hz, oTol ipso ), 131.3 (d, 3 J CP = 4.9 Hz, oTol ortho ), 131.0 (d, 4 J CP = 3.2 Hz, oTol meta ), 128.2 (d, 4 J CP = 3.6 Hz, oTol meta ), 126.4 (d, 3 J CP = 10.5 Hz, oTol ortho’ ), 126.1 (d, 5 J CP = 3.3 Hz, oTol para ), 66.5 (d, 2 J CP = 3.0 Hz, Cy(NCH3)2, C1), 65.7 (d, 2 J CP = 2.7 Hz, Cy(NCH3)2, C1), 36.5 (d, 1 J CP= 57.2 Hz, Cy, C1), 30.4 (d, 2 J CP = 4.3 Hz, NCH3), 30.2 (d, 2 J CP = 5.0 Hz, NCH3), 28.8 (d, 1 J CP = 52.9 Hz, CH2oTol), 27.77 (d, 3 J CP = 1.8 Hz, Cy(NCH3)2, C2), 27.71 (d, 3 J CP =1.4Hz, Cy(NCH3)2, C2'), 25.9 (d, 3 J CP = 4.0 Hz, Cy, C3), 25.7 (d, 3 J CP = 14.2 Hz, Cy, C3), 25.5-25.3 (m, Cy, C2+4), 23.6 (d, 4 J CP = 1.8 Hz, Cy(NCH3)2, C3), 20.8 (d, 4 J CP = 1.4 Hz, CH3)ppm. 31 P{ 1 H} NMR (162 MHz, 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: C 54.32, H 7.46, N 5.76; Found: C 54.22, H 7.32, N 5.61.

[0220] Synthesis of 16·H2:

[0221] [ka]

[0222] 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 formed and was filtered. The off-white solid was washed with THF (3 × 20 mL) and DCM (3 × 10 mL). The phosphonium salt 16·H2 was obtained as a colorless solid after drying in vacuo at 100 °C for 10 h. 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.

[0223] Yield: (4.54 g, 8.70 mmol, 84%).

[0224] 1 H NMR (400 MHz, CD3CN): δ = 6.97 - 6.84 (m, 4H, oTol), 3.51 (d, 1 J HP = 15.5 Hz, 2H, CH2oTol), 3.24- 3.20 (m, 12H, Mor, H2), 2.81 - 2.72 (m, 12H, Mor, H3), 2.06 (d, 3 J HH = 1.4 Hz, 3H, CH3)ppm. 13 C{ 1 H} NMR (101 MHz, CD3CN): δ = 138.6 (d, 2 J CP = 8.6 Hz, oTol ipso ), 132.4 (d, 4 J CP = 2.2 Hz, oTol meta ), 131.0 (d, 3 J CP = 5.1 Hz, oTol ortho ), 129.5 (d, 4 J CP= 3.2 Hz, oTol meta’ ), 128.1 (d, 3 J CP = 7.4 Hz, oTol ortho’ ), 127.8 (d, 5 J CP = 3.0 Hz, oTol para ), 66.9 (d, 2 J CP = 5.3 Hz, Mor, C2), 46.5 (Mor, C3), 26.3 (d, 1 J CP = 105.7 Hz, CH2oTol), 20.9 (CH3)ppm. 31 P{ 1 H} NMR (162 MHz, 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℃. 20 H 33 Elemental analysis for IN3O3P: Calculated: C 46.07, H 6.38, N 8.06; Found: C 45.92, H 8.08, N 6.37.

[0225] Synthesis of 17·H2:

[0226] [ka]

[0227] Tris(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 formed, which separated from the brown solution. Acetonitrile (30 mL) was added, and the resulting brown solution was treated with EtO (100 mL). The crude 17·H was obtained as a brown solid after filtration and was used without further purification.

[0228] Synthesis of 18·H2:

[0229] [ka]

[0230] Iminobibenzyl (1.95 g, 10 mmol) was dissolved in THF (25 ml) and slowly treated with n-BuLi (1.6 M, 4.25 ml, 10 mmol) at −90° C. The resulting colorless suspension was stirred at −90° C. for 1 h, after which iPr2PCl (1.53 ml, 10 mmol) was added and the reaction mixture was allowed to warm to room temperature. Benzyl bromide was added and the resulting colorless suspension was stirred overnight. The colorless solid was filtered and washed with THF (3 × 10 ml). The product was used in the next step without further purification.

[0231] Ligand synthesis and characterization:

[0232] L1 synthesis:

[0233] [ka]

[0234] 5 g (11 mmol, 1 equiv.) of the phosphonium salt 1·H2 was suspended in 50 ml of THF and deprotonated by slowly adding 6.9 ml of n-BuLi solution (1.6 M in hexane, 11 mmol, 1 equiv.) until a clear, slightly yellow solution was formed. The solution was stirred for 45 minutes, and then 2.42 ml (11 mmol, 1 equiv.) of each chlorophosphine was added at room temperature. A colorless solid precipitated immediately after addition. The suspension was stirred for 2 hours, and then 6.9 ml of n-BuLi solution (1.6 M in hexane, 11 mmol, 1 equiv.) was slowly added until a clear, yellow solution was formed. The solution was stirred for 30 minutes, after which the solvent was removed in vacuo. The residue was suspended in 50 ml of acetonitrile and stirred overnight, forming a colorless solid. The solid was filtered, washed with 2×20 ml of acetonitrile and dried in vacuo to give L1 (4.87 g, 8.55 mmol, 78%) as a colorless solid.

[0235] 1 H-NMR (400 MHz, CD2Cl2): δ = 0.96 - 1.36 (m, 10H, PCy2CH2H 2+3+4 ), 1.49 (q, 12H, 3 J=5.4Hz, Pip CH2H2), 1.53 - 1.59 (m, 6H, Pip CH2H3), 1.59 - 1.68 (m, 6H, PCy2CH2H 2+3+4 ), 1.69 - 1.77 (m, 2H, PCy2CH2H 2+3+4 ), 1.80 - 1.89 (m, 3H, PCy2CH2H 2+3+4 ), 2.18 (tdt, 2 J HP =10.6 Hz, 4 J HP = 6.4 Hz, 3 J=3.2Hz, 2H, PCy2CH H1), 3.07 (q, 3 J HP = 5.4 Hz, 6H, Pip CH2H1), 6.47 (m, 1H, Ph para ), 6.88 (m, 2H, Ph ortho), 6.98 (m, 2H, Ph meta ). 13 C-NMR (101 MHz, Methylene-d2 Chloride): δ = 25.4 (s, Pip CH2C3), 26.9 (d, 3 J CP = 4.7Hz, Pip CH2C2), 27.2 (d, 2 J=1.4Hz, PCy2CH​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​]: 2915 (m), 2841 (w), 1589 (w), 1485 (w), 1232 (m), 1155 (m), 1116 (w), 1059 (s), 1024 (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 / zC 34 H 58 N3P2[M+H] + , Calculated value: 570.4101, Measured value: 570.4092.

[0236] L2 synthesis:

[0237] [ka]

[0238] 2.7 g (6.15 mmol, 1 equiv.) of the phosphonium salt 2·H2 was suspended in 40 ml of THF and deprotonated by slowly adding 4 ml of n-BuLi solution (1.55 M in hexane, 6.15 mmol, 1 equiv.) until a clear solution was formed. The solution was stirred for 45 minutes, and then 1.36 ml of dicyclohexylchlorophosphine (6.15 mmol, 1 equiv.) was added at room temperature. A colorless solid precipitated immediately after addition. The suspension was stirred for 2 hours, and then 4 ml of n-BuLi solution (1.55 M in hexane, 6.15 mmol, 1 equiv.) was slowly added until a clear yellow solution was formed. The solution was stirred for 30 minutes, after which the solvent was removed in vacuo. The residue was suspended in 30 ml of acetonitrile and stirred overnight, forming a colorless solid. The solid was filtered, washed with 2×10 ml of acetonitrile and dried in vacuo, thus giving L2 (2.71 g, 5.34 mmol, 89%) as a colorless solid.

[0239] 1 H NMR (400 MHz, THF): δ = 3.08 (q, 3J = 5.2 Hz, 12H, Pip Pos.1, CH2), 1.86 (d, 3 J = 11.7 Hz, 2H, Cy Pos.3, CH2), 1.78 - 1.63 (m, 10H, Cy Pos.1, CH + Cy Pos.2 + Pos.3, CH2), 1.61 - 1.42 (m, 21H, CH3+ Pip Pos.2 + Pos.3, CH2), 1.33 - 1.11 (m, 10H, Cy Pos.3 + Pos.2, CH2). 13 C NMR (101 MHz, THF): δ = 48.6 (d, 2 J CP = 5.1 Hz, Pip Pos. 1, CH2), 35.6 (dd, 1 J CP = 13.8 Hz, 3 J CP = 8.8 Hz, Cy Pos.1, CH), 33.3 (d, 2 J CP = 19.9 Hz, Cy Pos.2, CH2), 32.2 (d, 3 J CP = 9.2 Hz, Cy Pos.3, CH2), 29.1 (d, 3 J CP = 6.9 Hz, Cy Pos.3, CH2), 28.9 (d, 2 J CP = 12.4 Hz, Cy Pos.2, CH2), 28.3 (s, Cy Pos.4, CH2), 27.9 (d, 3 J CP = 5.2 Hz, Pip Pos.2, CH2), 26.3 (s, Pip Pos.3, CH2), 15.4 (d, 2 J CP = 9.7 Hz, CH3), 13.5 (dd, 1 J CP = 195.5, 19.8 Hz, P-C - -P). 31 P NMR (162 MHz, THF): δ = 60.9 (d, 2 JPP = 191.8 Hz, P + Pip3), -4.3 (d, 2 J PP = 192.0 Hz, 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), 1048 (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 / zC 29 H 56 N3P2[M+H] + , Calculated value: 508.3944, Measured value: 508.3936.

[0240] Synthesis of L3:

[0241] [ka]

[0242] 4.5 g (12.1 mmol, 1 equiv.) of the phosphonium salt 3·H2 was suspended in 50 ml of THF and deprotonated by slowly adding 7.8 ml of n-BuLi solution (1.55 M in hexane, 12.1 mmol, 1 equiv.) until a clear, slightly yellow solution was formed. The solution was stirred for 45 minutes, and then 2.67 ml of dicyclohexylchlorophosphine (12.1 mmol, 1 equiv.) was added at room temperature. A colorless solid precipitated immediately after addition. The suspension was stirred for 2 hours, and then 7.8 ml of n-BuLi solution (1.55 M in hexane, 12.1 mmol, 1 equiv.) was slowly added until a clear, yellow solution was formed. The solution was stirred for 30 minutes, after which the solvent was removed in vacuo. The residue was suspended in 50 ml of acetonitrile and stirred overnight, forming a colorless solid. The solid was filtered, washed with 2×20 ml of acetonitrile and dried in vacuo, thus giving L3 (4.26 g, 8.76 mmol, 72%) as a colorless solid.

[0243] 1 H NMR (400 MHz, C6D6): δ = 7.33 - 7.27 (m, 4H, Ph ortho + Ph meta CH), 7.04 - 6.97 (m, 1H, Ph para CH), 3.27 (br, 1H, P + Cy Pos. 1 CH), 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, PCy2Pos. 2 CH2), 2.17 - 1.96 (m, 6H, PCy2Pos. 1 CH + Pos. 3 CH2), 1.88 - 1.78 (m, 4H, P + Cy Pos. 3 CH2), 1.77 - 1.65 (m, 4H, PCy2Pos. 2 CH2), 1.65 - 1.50 (m, 4H, P +Cy Pos. 2 + Pos. 4 CH2), 1.46 - 1.10 (m, 12H, P + Cy Pos. 2 + PCy2Pos. 2 + Pos. 3 + Pos. 4 CH2). 13C NMR (101 MHz, C6D6): δ = 144.8 (dd, 2 J CP = 5.6, 3.3Hz, Ph ypso C), 129.6 (s, Ph meta ), 127.5 (s, Ph ortho ), 121.7 (s, Ph para ), 48.0 (d, 2 J CP = 5.1 Hz, MeN(CH2)2NMe), 37.8 (dd, 1 J CP = 90.8 Hz, 3 J CP = 18.0 Hz, P + Cy Pos. 1 CH), 36.9 (dd, 1 J CP = 13.5 Hz, 3 J CP = 8.1 Hz, PCy2Pos. 1 CH2), 34.3 (dd, 1 J CP = 131.3, 30.5 Hz, P-C - -P), 33.1 (d, 2 J CP = 6.3 Hz, NCH3), 32.7 (d, 2 J CP = 20.2 Hz, P + Cy Pos. 2 CH2), 30.9 (d, 3 J CP = 8.8 Hz, PCy2Pos. 3 CH2), 28.0 (d, 3 J CP = 7.7 Hz, PCy2Pos. 3 CH2), 27.7 (d, 3 J CP = 12.5 Hz, P + Cy Pos. 3 CH2), 27.1 (s, PCy2Pos. 4 CH2), 26.5 (d,2 J CP = 14.0 Hz, PCy2Pos. 2 CH2), 26.2 (s, P + Cy Pos. 4 CH2). 31P NMR (162 MHz, C6D6): δ = 62.9 (d, 2 J PP = 177.5 Hz, 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 / zC 29 H 49 N2P2[M+H] + , Calculated value: 487.3433, Measured value: 487.3358.

[0244] Synthesis of L4:

[0245] [ka]

[0246] 2.6 g (7.3 mmol, 1 equiv.) of the phosphonium salt 4·H2 was suspended in 30 ml of THF and deprotonated by slowly adding 4.7 ml of n-BuLi solution (1.55 M in hexane, 7.3 mmol, 1 equiv.) until a clear, slightly yellow solution was formed. The solution was stirred for 45 minutes, and then 1.61 ml of dicyclohexylchlorophosphine (7.3 mmol, 1 equiv.) was added at room temperature. A colorless solid precipitated immediately after addition. The suspension was stirred for 2 hours, and then 4.7 ml of n-BuLi solution (1.55 M in hexane, 7.3 mmol, 1 equiv.) was slowly added until a clear, yellow solution was formed. The solution was stirred for 30 minutes, after which the solvent was removed in vacuo. The residue was suspended in 30 ml of acetonitrile and stirred overnight, forming a colorless solid. The solid was filtered, washed with 2×10 ml of acetonitrile and dried in vacuo, thus giving L4 (2.22 g, 5.22 mmol, 72%) as a colorless solid.

[0247] 1 H NMR (400 MHz, C6D6): δ = 3.06 (s, 1H, P + Cy Pos. 1 CH), 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, PCy2Pos. 3 CH2), 2.13 - 2.03 (m, 4H, P + Cy Pos. 2 + PCy2Pos. 2 CH2), 2.02 - 1.85 (m, 6H, PCy2Pos. 1 CH + PCy2Pos. 2 + Pos. 3 CH2), 1.80 - 1.74 (m, 2H, PCy2Pos. 4 CHH2), 1.74 - 1.66 (m, 2H, P + Cy Pos. 3 CH2), 1.65 - 1.06 (m, 24H, P + Cy Pos. 2 + Pos. 3 + Pos. 4 CH2+ PCy2Pos. 2 + Pos. 3 + Pos. 4 CH2).13 C NMR (101 MHz, C6D6): δ = 48.5 (d, 2 J CP = 4.8 Hz, MeN(CH2)2NMe), 36.7 (dd, 1 J CP = 88.0 Hz, 3 J CP = 14.3 Hz, P + Cy Pos. 1 CH), 35.6 (dd, 1 J CP = 12.5 Hz, 3 J CP = 8.3 Hz CH), 33.6 (d, 2 J CP = 6.1 Hz, NMe), 32.9 (d, 2 J CP = 20.5 Hz, PCy2Pos. 2 CH2), 31.6 (d, 3 J CP = 7.4 Hz, PCy2Pos. 3 CH2), 28.7 (dd, 2 J CP = 6.3, 4 J CP = 4.6 Hz, P + Cy Pos. 2 CH2), 28.5 (d, 3 J CP = 6.6 Hz, PCy2Pos. 3 CH2), 28.3 (d, 2 J CP = 12.8 Hz, PCy2Pos. 2 CH2), 27.6 (s, PCy2Pos. 4 CH2), 26.8 (d, 3 J CP = 13.7 Hz, PCy2Pos. 3 CH2), 26.6 (d, 4 J CP = 1.8 Hz, P + Cy Pos. 4 CH2), 17.0 (dd, 1 J CP = 140.4, 21.8 Hz, PC - -P), 11.8 (dd, 2 J CP = 4.8, 2.4 Hz, PC- -CH3). 31 P NMR (162 MHz, C6D6): δ = 68.6 (d, 2 J PP = 172.0 Hz, P + Cy), -2.9 (d, 2 J PP = 171.4 Hz, 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 / zC 24 H 47 N2P2[M+H] + , Calculated value: 425.3209, Measured value: 425.3204.

[0248] Synthesis of L5:

[0249] [ka]

[0250] 1 g (2.14 mmol, 1 equiv.) of the phosphonium salt 5·H2 was suspended in 10 ml of THF and deprotonated by slowly adding 1.38 ml of n-BuLi solution (1.55 M in hexane, 2.14 mmol, 1 equiv.) until a clear, slightly yellow solution was formed. The solution was stirred for 45 minutes, and then 0.47 ml of dicyclohexylchlorophosphine (2.14 mmol, 1 equiv.) was added at room temperature. A colorless solid precipitated immediately after addition. The suspension was stirred for 2 hours, and then 1.38 ml of n-BuLi solution (1.55 M in hexane, 2.14 mmol, 1 equiv.) was slowly added until a clear, yellow solution was formed. The solution was stirred for 30 minutes, after which the solvent was removed in vacuo. The residue was suspended in 30 ml of acetonitrile and stirred overnight, forming a colorless solid. The solid was filtered, washed with 2×15 ml of acetonitrile and dried in vacuo, thus giving L5 (1 g, 2.14 mmol, 87%) as a colorless solid.

[0251] 1 H NMR (400 MHz, C6D6): δ = 3.10 (q, J HH = 5.1 Hz, 12H, Pip Pos. 1 CH2), 2.76 (tdd, 3 J HP = 13.8, 11.2 Hz, J HH = 6.9 Hz, 1H, iPr CH3), 2.42 - 2.29 (m, 2H, Cy Pos. 2 CH2), 2.23 - 2.09 (m, 4H, Cy Pos. 2 CH2+ Pos. 1 CH), 2.02 - 1.87 (m, 4H, Cy Pos. 3 CH2), 1.85 - 1.76 (m, 2H,Cy Pos. 4 CH2), 1.56 - 1.34 (m, 34H, Pip Pos. 2 + Pos. 3 CH2+ Cy Pos. 4 CH2+ iPr CH3). 13 C NMR (101 MHz, C6D6): δ = 48.8 (d, 2 J CP = 5.9 Hz, Pip Pos. 1 CH2), 37.8 (dd, 1J CP = 31.4, 3 J CP = 17.3 Hz, Cy Pos. 1 CH), 33.7 (dd, 2 J CP = 16.5, 4 J CP = 10.0 Hz, Cy Pos. 2 CH2), 31.9 (dd, 2 J CP = 13.3, 1.9 Hz, iPr CH), 30.0 (dd, 1 J CP = 177.3, 29.3 Hz, PC - -P), 28.6 (dd, 3 J CP = 24.6, 10.5 Hz, Cy Pos. 3 CH2), 27.7 (s, Pip Pos. 2 CH2), 27.0 (d, 4 J CP = 4.7 Hz, Cy Pos. 4 CH2), 26.3 (d, 3 J CP = 7.7 Hz, iPr CH3), 25.6 (s, Pip Pos. 3 CH2). 31 P NMR (162 MHz, C6D6): δ = 61.2 (d, 2 J PP = 215.8 Hz, P(Pip)3), −0.3 (d, 2 J PP = 215.9 Hz, PCy2). IR(ATR)[cm -1 ]: 3676 (w), 3399 (w), 2914 (w), 2839 (w), 1637 (w), 1437 (w), 1324 (w), 1204 (w), 1153 (w), 1110 (w), 1041 (w), 9381 (w), (w), 664 (w), 592 (w), 553 (w), 530 (w), 462 (w). HRMS(ESI):m / zC 31 H 60 N3P2[M+H] +, Calculated value: 536.4257, Measured value: 536.4253.

[0252] Synthesis of L6:

[0253] [ka]

[0254] 1.92 g (4.36 mmol, 1 equiv.) of the phosphonium salt 2·H2 was suspended in THF and deprotonated by slowly adding 2.81 ml of n-BuLi solution (1.55 M in hexane, 4.36 mmol, 1 equiv.) until a clear, slightly yellow solution was formed. The solution was stirred for 45 min, and then 0.43 ml of di-tert-butylchlorophosphine (2.18 mmol, 0.5 equiv.) was added at room temperature. The solution was stirred at reflux for 16 h, during which time the reformed phosphonium salt precipitated as a white solid. The solid was filtered, and the solution solvent was removed in vacuo. The residue was suspended in 20 ml of acetonitrile and stirred overnight to form a colorless solid. The solid was filtered, washed with 2 × 15 ml of acetonitrile, and dried in vacuo, thus yielding L6 (587 mg, 1.29 mmol, 59%) as a colorless solid.

[0255] 1 H NMR (400 MHz, C6D6): δ = 3.04 (q, J HH = 5.1 Hz, 12H, Pip Pos. 1), 1.98 (dd, 3 J HP = 15.4, 3.0 Hz, 3H, PC - -CH3), 1.53 (d, 3 J HP = 10.8Hz, 18H, t Bu CH3), 1.30 - 1.45 (m, 18H, Pip Pos. 2 + Pos. 3 CH2). 13 C NMR (101 MHz, C6D6): δ = 47.9 (d, 2 J CP= 4.8 Hz, Pip Pos. 1 CH2), 36.0 (dd, 1 J CP = 23.4 Hz, 3 J CP = 10.7 Hz, t Bu C(CH3)3), 33.0 (d, 2 J CP = 15.2 Hz, t Bu C(CH3)3), 27.1 (d, 3 J CP = 5.0 Hz, Pip Pos. 2 CH2), 25.5 (d, 4 J CP = 1.2 Hz, Pip Pos. 3 CH2), 17.5 (d, 2 J CP = 9.9 Hz, PC - -CH3), 16.9 (dd, 1 J CP = 191.5, 25.3 Hz, PC - -P). 31P NMR (162 MHz, C6D6): δ = 60.8 (d, 2 J PP = 208.5 Hz, P(Pip)3), 25.3 (d, 2 J PP = 208.9 Hz, 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 / zC 25 H 52 N3P2[M+H] + , calculated value: 456.3631, measured value: 456.3625.

[0256] Synthesis of L7:

[0257] [ka]

[0258] 6.5 g (12.6 mmol, 1 equiv.) of the phosphonium salt 7·H2 was suspended in 70 ml of THF and deprotonated by slowly adding 8.4 ml of n-BuLi solution (1.5 M in hexane, 12.6 mmol, 1 equiv.) until a clear, slightly yellow solution was formed. The solution was stirred for 45 minutes, and then 3.34 ml of dicyclohexyl iodophosphine (15.1 mmol, 1.1 equiv.) was added at room temperature. A colorless solid precipitated immediately after addition. The suspension was stirred for 2 hours, and then 8.4 ml of n-BuLi solution (1.5 M in hexane, 12.6 mmol, 1 equiv.) was slowly added until a clear, yellow solution was formed. The solution was stirred for 30 minutes, after which the solvent was removed in vacuo. The residue was suspended in 75 ml of acetonitrile and stirred overnight, forming a colorless solid. The solid was filtered, washed with 5×15 ml of acetonitrile and dried in vacuo, thus giving L7 (5 g, 8.65 mmol, 69%) as a colorless solid.

[0259] 1 H NMR (400 MHz, C6D6): δ = 7.49 - 7.41 (m, 1H, Tol. Pos. 6 CH), 7.31 - 7.26 (m, 1H, Tol. Pos. 4 CH), 7.20 - 7.13 (m, 1H, Tol, Pos. 3 CH), 7.13 - 7.07 (m, 1H, Tol. Pos. 5 CH), 2.94 (q, J HH= 4.7 Hz, 12H, Pip Pos. 1 CH2), 2.71 (s, 3H, Tol CH3), 2.53 - 2.45 (m, 2H, Cy Pos. 2 CH2), 2.00 - 1.87 (m, 4H, Cy Pos. 1 CH + Pos. 3 CH2), 1.78 - 1.71 (m, 4H, Cy Pos. 4 CH2), 1.69 - 1.64 (m, 2H, Cy Pos. 3 CH2), 1.59 - 1.30 (m, 28H, Pip Pos. 2 + Pip Pos. 3 + Cy Pos. 2 + Cy Pos. 3 CH2). 13 C NMR (101 MHz, C6D6): δ = 143.3 (dd, 2 J CP = 12.7, 2.7 Hz, Tol. Pos. 1 C), 142.0 (d, 3 J CP = 8.0 Hz, Tol. Pos. 2 C), 138.2 (d, 3 J CP = 5.6 Hz, Tol. Pos. 6 CH), 130.3 (s, Tol. Pos. 4 CH), 124.7 (d, 4 J CP = 2.7Hz, Tol. Pos. 3 CH), 124.6 (d, 4 J CP = 2.4 Hz, Tol. Pos. 5 CH), 47.9 (d, 2 J CP = 3.8 Hz, Pip Pos. 1 CH2), 39.0 (dd, 1 J CP = 16.1 Hz, 3 J CP = 7.9 Hz, Cy Pos. 1 CH), 34.7 (d, 2 J CP = 22.4 Hz, Cy Pos. 2 CH2), 30.8 (d, 3 J CP = 7.3 Hz, Cy Pos. 3 CH2), 30.0 (dd, 1 J CP= 186.6, 28.5 Hz, PC - -P), 29.1 (d, 3 J CP = 13.6 Hz, Cy Pos. 3 CH2), 27.5 (s, Cy Pos. 4 CH2), 26.8 (d, 3 J CP = 5.4 Hz, Pip Pos. 2 CH2), 25.5 (s, Pip Pos. 3 CH2), 22.9 (s, Tol. CH3). 31 P NMR (162 MHz, C6D6): δ = 51.6 (d, 2 J PP = 160.3 Hz, P(Pip)3), -1.3 (d, 2 J PP = 160.0 Hz, 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, Measured value: 584.4249.

[0260] Synthesis of L8:

[0261] [ka]

[0262] 3.8 g (8.64 mmol, 1 equiv.) of the phosphonium salt 2·H2 was suspended in 25 ml of THF and deprotonated by slowly adding 5.72 ml of n-BuLi solution (1.51 M in hexane, 8.64 mmol, 1 equiv.) until a clear, slightly yellow solution was formed. The solution was stirred for 45 minutes, and then a solution of 1.5 g of diadamantylchlorophosphine (4.32 mmol, 0.5 equiv.) in 10 ml of THF was added at room temperature. The solution was stirred at reflux for 16 hours, during which time the reformed phosphonium salt precipitated as a white solid. The solid was filtered, and the solution solvent was removed in vacuo. The residue was suspended in 25 ml of acetonitrile and stirred overnight to form a colorless solid. The solid was filtered, washed with 2×15 ml of acetonitrile and dried in vacuo, thus giving L8 (1.87 g, 4.32 mmol, 71%) as a colorless solid.

[0263] IR(ATR)[cm 1 ]: 2898 (m), 2844 (w), 2673 (w), 1447 (w), 1368 (w), 1325 (w), 1258 (w), 1213 (w), 1154 (w), 1118 (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).

[0264] Synthesis of L9:

[0265] [ka]

[0266] 3.0 g (5.82 mmol, 1 equiv.) of the phosphonium salt 7·H2 was suspended in 20 ml of THF and deprotonated by slowly adding 3.88 ml of n-BuLi solution (1.6 M in hexane, 5.82 mmol, 1 equiv.) until a clear, slightly yellow solution was formed. The solution was stirred for 45 minutes, and then 1.02 ml of diisopropyliodophosphine (6.4 mmol, 1.1 equiv.) was added at room temperature. A colorless solid precipitated immediately after addition. The suspension was stirred for 2 hours, and then 3.88 ml of n-BuLi solution (1.6 M in hexane, 5.82 mmol, 1 equiv.) was slowly added until a clear, yellow solution was formed. The solution was stirred for 30 minutes, after which the solvent was removed in vacuo until approximately 3 ml remained. 40 ml of acetonitrile was added to the residue, which was stirred overnight to form a colorless solid. The solid was filtered, washed with 5×5 ml of acetonitrile and dried in vacuo, thus giving L9 (1.71 g, 3.39 mmol, 59%) as a colorless solid.

[0267] General procedure for the synthesis of L10-L17: The phosphonium salt (1 equiv.) was suspended in THF (75 ml). A solution of n-BuLi in hexane (1.6 M, 1 equiv.) was slowly added. The solution was stirred at room temperature for 1 hour, after which dialkyliodophosphine (1.2 equiv.) in pentane (75 ml) was added. The reaction mixture was stirred for 2 hours, and the colorless precipitate formed was filtered and washed with pentane (3 × 20 ml). The solid was dried in vacuo, KOtBu (1.5 equiv.) was added, and the mixture was stirred overnight in toluene (100 ml). The solvent was removed in vacuo, and the residue was resuspended in pentane (200 ml). The mixture was filtered on a Celite plug, and the residue was extracted with pentane (3 × 50 ml). The solvent was removed in vacuo, and the residue was stirred in acetonitrile (150 ml) until a finely dispersed colorless solid was obtained. The colourless solid was filtered and washed with acetonitrile (3 x 50 ml) to give the product.

[0268] Synthesis of L10:

[0269] [ka]

[0270] Phosphine L10 was synthesized from 10·H2 (2.02 g, 4.67 mmol) according to the general procedure for the P,N-YPhos ligand. Colorless crystals suitable for single-crystal X-ray diffraction experiments were obtained by slow evaporation of a saturated benzene solution.

[0271] Yield: (1.25g, 2.50mmol, 54%).

[0272] 1 H NMR (400 MHz, C6D6): δ = 7.37 (d, 3 J HH = 7.6 Hz, 1H, oTol ortho ), 7.25 (d, 3 J HH = 7.4 Hz, 1H, oTol meta ), 7.14 - 7.04 (m, 2H, oTol meta’+para ), 2.80 - 2.67 (m, 3H, NC2H4N+Cy, H1), 2.67 - 2.62 (m, 5H, NC2H4N+CH3), 2.50 (d, 3 J HP = 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. 13 C{ 1 H} NMR (101 MHz, C6D6): δ = 142.6 (dd, 2 J CP = 9.7, 4.3 Hz, oTol ipso), 140.4 (d, 3 J CP = 7.0 Hz, oTol ortho ), 137.2 (d, 3 J CP = 6.8 Hz, oTol ortho’ ), 130.6 (d, 4 J CP = 1.7 Hz, oTol meta ), 124.9 (t, J = 2.4 Hz, oTol meta+para ), 48.5 (d, 2 J CP = 4.7 Hz, NC2H4N), 39.0 (dd, 1 J CP = 85.6, 3 J CP = 13.8 Hz, Cy, C1), 37.2 (brs, PCy2, C1), 34.0 (dd, 1 J CP = 134.3, 31.8 Hz, PCP), 33.9 (d, 2 J CP = 6.0 Hz, NCH3), 32.8 (d, 2 J CP = 18.6 Hz, Cy, C2), 30.9 (d, 3 J CP = 9.6 Hz, PCy2, C3), 28.7 - 28.4 (m, PCy2, C2+3), 28.2 (d, 3 J CP = 7.8 Hz, Cy, C3), 27.5 (s, PCy2, C4), 27.2 (d, 2 J CP = 13.4 Hz, PCy2, C2), 26.7 (d, 4 J CP = 1.5 Hz, Cy, C4), 22.6 (s, CH3, oTol)ppm. 31 P{ 1 H} NMR (162 MHz, C6D6): δ = 57.8 (d, 2 J PP = 161.3 Hz, 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 for N2P2: Calculated: C 71.97, H 10.07, N 5.59; Found: C 72.06, H 10.29, N 5.56.

[0273] Synthesis of L11:

[0274] [ka]

[0275] Phosphine L11 was synthesized from 11·H2 (12.25 g, 25.1 mmol) according to the general procedure for the P,N-YPhos ligand. Colorless crystals suitable for single-crystal X-ray diffraction experiments were obtained by slow evaporation of a saturated benzene solution.

[0276] Yield: (12.4 g, 22.2 mmol, 88%).

[0277] NMR spectroscopy was carried out at 70°C. 1 H NMR (400 MHz, C6D6): δ = 7.36 (d, 3 J HH = 7.5 Hz, 1H, oTol ortho ), 7.13 (d, 3 J HH = 6.4 Hz, 1H, oTol meta ), 7.06 - 6.93 (m, 2H, oTol meta’+para), 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 = 6.6 Hz, 6H, CH3, iPr), 0.90 - 0.75 (m, 6H, CH3, iPr)ppm. 13 C{ 1 H} NMR (101 MHz, C6D6): δ = 143.9 (dd, 2 J CP = 6.7, 3.4 Hz, oTol ipso ), 140.7 (d, 3 J CP = 9.8 Hz, oTol ortho ), 136.0 (d, 3 J CP = 7.3 Hz, oTol ortho’ ), 130.6 (s, oTol para ), 124.8 (d, 4 J CP = 1.5 Hz, oTol meta ), 124.4 (d, 4 J CP = 2.0 Hz, oTol meta’ ), 43.9 (dd, 2 J CP = 7.1 Hz, 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 =1.6Hz, 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 =168.2Hz, 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. 34 H 58 Elemental analysis for N2P2: Calculated: C 73.34, H 10.50, N 5.03; Found: C 72.98, H 10.67, N 4.96.

[0278] Synthesis of L12:

[0279] [ka]

[0280] Phosphine L12 was synthesized from 12·H2 (8.23 g, 15.1 mmol) according to the general procedure for the P,N-YPhos ligand. Colorless crystals suitable for single-crystal X-ray diffraction experiments were obtained by slow evaporation of a saturated hexane solution.

[0281] Yield: (7.51 g, 12.25 mmol, 81%).

[0282] NMR spectroscopy was carried out at 70°C. 1 H NMR (400 MHz, C6D6): δ = 7.42 (d, 3 J HH = 7.5 Hz, 1H, oTol ortho ), 7.20 (d, 3 J HH = 7.4 Hz, 1H, oTol meta ), 7.09 (t, 3 J HH = 7.2 Hz, 1H, oTol meta’ ), 7.03 (t, 3 J HH = 7.3 Hz, 1H, oTol para ), 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, 2.7 Hz, 12H, CH3, iPen)ppm. 13 C{ 1H} NMR (101 MHz, C6D6): δ = 143.2 (dd, 2 J CP = 10.8, 3.8 Hz, oTol ipso ), 140.5 (d, 3 J CP = 8.0 Hz, oTol ortho ), 137.0 (d, 3 J CP = 6.8 Hz, oTol ortho’ ), 130.66 (d, 4 J CP = 0.9 Hz, oTol meta ), 125.1 (d, 4 J CP = 1.7Hz, oTol meta’ ), 124.8 (d, 5 J CP = 2.3 Hz, oTol para ), 46.1 (dd, 2 J CP = 4.8 Hz, 4 J CP = 1.2 Hz, NCH2), 45.8 (dd, 2 J CP = 5.2 Hz, 4 J CP = 1.9 Hz, NC2H4N), 40.20 (dd, 1 J CP = 86.3 Hz, 3 J CP = 12.7 Hz, Cy, C1), 38.6 (d, 3 J CP =5.4 Hz, CH2, iPen), 38.1 (dd, 1 J CP = 15.5 Hz, 3 J CP = 8.1 Hz, PCy2, C1), 35.5 (dd, 1 J CP = 130.3, 31.4Hz, PCP), 33.9 (d, 2 J CP = 21.5 Hz, Cy, C2), 31.0 (d, 3 JCP = 8.1 Hz, PCy2, C3), 28.9 - 28.6 (m, PCy2, C2+3), 28.2 (d, 3 J CP = 6.7 Hz, Cy, C3), 27.6 - 27.3 (m, PCy2, C2+4), 27.2 (s, CH(CH3)2), 26.9 (d, 4 J CP =1.6 Hz, Cy, C4), 23.0 (s, CH3, iPen), 22.8 (s, CH3, iPen), 22.5 (s, CH3, oTol)ppm. 31 P{ 1 H} NMR (162 MHz, C6D6): δ = 59.9 (d, 2 J PP = 157.2 Hz, PCy(iPenNC2H4NiPen)), -0.4 (d, 2 J PP =157.2 Hz, 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℃. 38 H 66 Elemental analysis for N2P2: Calculated: C 74.47, H 10.85, N 4.57; Found: C 74.62, H 11.23, N 4.54.

[0283] Synthesis of L13:

[0284] [ka]

[0285] Phosphine L13 was synthesized from 13·H2 (10.8 g, 23.1 mmol) according to the general procedure for the P,N-YPhos ligand. Colorless crystals suitable for single-crystal X-ray diffraction experiments were obtained by slow evaporation of a saturated hexane solution.

[0286] Yield: (8.35 g, 15.6 mmol, 67%).

[0287] 1 H NMR (400 MHz, C6D6): δ = 3.18 (dd, 3 J HP = 13.8, 5 J HP = 7.4 Hz, 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 = 5.2 Hz, 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, 3.0 Hz, 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 (101 MHz, C6D6): δ = 60.1 (d, 2 J CP = 4.4 Hz, NCH2tBu), 49.1 (d, 2 J CP = 5.6 Hz, NC2H4N), 38.9 (dd, 1 J CP = 87.3, 3J CP = 8.8 Hz, Cy, C1), 35.7 (dd, 1 J CP = 13.2, 3 J CP = 8.1 Hz, PCy2, C1), 33.6 (d, 3 J CP = 6.4 Hz, C(CH3)3), 32.8 (d, 2 J CP = 19.3 Hz, Cy, C2), 32.1 (d, 3 J CP = 8.8 Hz, PCy2, C3), 29.6 - 29.2 (m, C(CH3)3+Cy, C3), 28.4 (d, 3 J CP = 7.1 Hz, PCy2, C3'), 28.2 (d, 2 J CP = 12.2 Hz, PCy2, C2), 27.6 (s, PCy2, C4), 27.1 (d, 2 J CP = 13.7 Hz, PCy2, C2'), 27.0 (d, 4 J CP = 1.5 Hz, 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 = 1.5 Hz, PCPCH3)ppm. 31 P{ 1 H} NMR (162 MHz, C6D6): δ = 79.3 (d, 2 J PP = 167.4 Hz, PCy(neoPenNC2H4NneoPen)), -3.9 (d, 2 J PP= 167.4 Hz, 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 for N2P2: Calculated: C 71.60, H 11.64, N 5.22; Found: C 71.46, H 11.85, N 5.18.

[0288] Synthesis of L14:

[0289] [ka]

[0290] Phosphine L14 was synthesized from 14·H2 (4.01 g, 7.11 mmol) according to the general procedure for the P,N-YPhos ligand. Colorless crystals suitable for single-crystal X-ray diffraction experiments were obtained by slow evaporation of a saturated benzene solution.

[0291] Yield (2.13 g, 3.85 mmol, 54%).

[0292] NMR spectroscopy was carried out at 70°C. 1 H NMR (400 MHz, C6D6): δ = 6.82 (s, 2H, Mes meta ), 6.79 (s, 2H, Mes meta’ ), 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 ortho ), 2.48 (s, 6H, CH3, Mes ortho’ ), 2.33 - 2.18 (m, 2H, Cy, H2), 2.10 (s, 6H, CH3, Mespara ), 2.07 to 1.94 (m, 4H, Cy, H2+CH(CH3)2), 1.78 (dd, 3 J HP = 16.9, 2.8 Hz, 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 = 13.0 Hz, 3 J HH = 7.0 Hz, 6H, CH3, iPr), 1.07 (dd, 3 J HP =12.4Hz, 3 J HH = 7.1 Hz, 6H, CH3, iPr)ppm. 13 C{ 1 H} NMR (101 MHz, C6D6): δ = 139.9 (d, 2 J CP = 5.4 Hz, We ipso ), 138.8 (d, 3 J CP = 1.5 Hz, We ortho ), 138.4 (d, 3 J CP = 2.0 Hz, We ortho’ ), 135.9 (s, We para ), 130.3 (s, We meta ), 130.1 (s, We meta’ ), 49.8 (d, 2 J CP = 7.3 Hz, NC2H4N), 44.9 (dd, 1 J CP = 87.2 Hz, 3 J CP = 7.4 Hz, Cy, C1), 29.8 (dd, 2 J CP = 16.7 Hz, 4 J CP =4.7 Hz, Cy, C2), 28.1 (d, 3 J CP= 13.8 Hz, Cy, C3), 26.7 (d, 4 J CP = 1.8 Hz, Cy, C4), 26.48 (dd, 1 J CP =140.1, 31.2 Hz, PCP), 24.7 (dd, 1 J CP = 15.1 Hz, 3 J CP = 9.1 Hz, CH(CH3)2), 21.9 (d, 2 J CP = 15.1 Hz, CH3, iPr), 21.5 (d, 2 J CP = 17.9 Hz, CH3, iPr), 21.0 (s. CH3, Mes ortho ), 20.7 (p. CH3, Mes para ), 20.4 (s, CH3, Mes ortho’ ), 15.7 (d, 1 J CP = 3.0 Hz, PCPCH3)ppm. 31 P{ 1 H} NMR (162 MHz, C6D6): δ = 50.2 (d, 2 J PP = 176.3 Hz, PCy(MesNC2H4NMes)), 8.3 (d, 2 J PP =176.3 Hz, 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), 625 (s), (m), 533 (w), 444 (m), 436 (m) cm -1 . Temperature:177°C 34 H 54 N2P2:C 73.88, H 9.85, N 5.07, C 73.52, H 9.85, N 4.91.

[0293] Synthesis of L15:

[0294] [ka]

[0295] Phosphine L15 was synthesized from 15·H2 (6.51 g, 13.4 mmol) according to the general procedure for the P,N-YPhos ligand, 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 a saturated hexane solution.

[0296] Yield: (4.93 mg, 8.88 mmol, 66%).

[0297] NMR spectroscopy was carried out at 70° C. In some cases, overlapping peaks from three different cyclohexyl moieties prevented NMR spectral assignment. 1 H NMR (400 MHz, C6D6): δ = 7.42 (d, 3 J HH = 7.4 Hz, 1H, oTol ortho ), 7.24 - 7.20 (m, 1H, oTol meta ), 7.11 - 7.01 (m, 2H, oTol meta’+para ), 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 (101 MHz, C6D6): δ = 142.7 (bs, oTol ipso ), 140.9 (d, 3 J CP = 7.4 Hz, oTol ortho ), 137.9 (d, 3 J CP= 6.2 Hz, oTol ortho’ ), 130.6 (d, 4 J CP = 1.7 Hz, oTol meta ), 125.0 (d, 4 J CP = 2.5 Hz, oTol meta’ ), 124.8 (d, 5 J CP = 2.0 Hz, oTol para ), 66.0 (s, Cy(NCH3)2, C1), 64.5 (d, 2 J CP = 4.1 Hz, Cy(NCH3)2, C1), 39.3 (dd, 1 J CP =82.1 Hz, 3 J CP = 13.7 Hz, Cy, C1+PCy2, C1), 36.2 (PCy2, C1), 35.1 (dd, 1 J CP = 132.8, 33.1 Hz, PCP), 33.4 (s, Cy(NCH3)2+Cy+PCy2), 32.7 (d, J = 18.2 Hz, Cy(NCH3)2+Cy+PCy2), 32.0 (s, NCH3), 31.4 (d, J=12.7 Hz, Cy(NCH3) 2+ Cy+PCy2), 30.5 (d, J = 6.0 Hz, Cy(NCH3)2+Cy+PCy2), 30.0 (t, J = 4.1 Hz, Cy(NCH3)2+Cy+PCy2), 29.9 (d, J = 7.3 Hz, Cy(NCH3)2+Cy+PCy2), 29.5 (d, 2 J CP= 5.8 Hz, NCH3), 29.2 - 28.9 (m, Cy(NCH3)2+Cy+PCy2), 28.6 (d, J = 6.5 Hz, Cy(NCH3)2+Cy+PCy2), 28.1 (dd, J = 31.1, 9.9 Hz, Cy(NCH3)2+Cy+PCy2), 27.8 - 27.3 (m, Cy(NCH3)2+Cy+PCy2), 26.8 (d, J = 1.5 Hz, Cy(NCH3)2+Cy+PCy2), 24.9 (d, J = 18.6 Hz, Cy(NCH3)2+Cy+PCy2), 22.8 (s, CH3, oTol) ppm. 31 P{ 1 H} NMR (162 MHz, C6D6): δ = 59.4 (d, 2 J PP = 152.2 Hz, 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. C 34 H 56 Elemental analysis of N2P2: Calculated: C 73.61, H 10.17, N 5.05; Found: C �3.74, H 10.43, N 5.05.

[0298] Synthesis of L16:

[0299]

Chem.

[0300] Phosphine L16 was synthesized from 16·H2 (1.44 g, 2.76 mmol) according to the general procedure for the P,N-YPhos ligand, except that filtration through a Celite plug 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.

[0301] Yield: (1.14 g, 1.93 mmol, 70%).

[0302] 1 H NMR (400 MHz, C6D6): δ = 7.25 (d, 3 J HH = 7.4 Hz, 1H, oTol para ), 7.20 (d, 3 J HH = 7.0 Hz, 1H, oTol ortho ), 7.13 - 7.03 (m, 2H, oTol ortho’+meta ), 3.37 (t, 3 J HH = 4.5 Hz, 12H, Mor, H2), 2.85 (q, 3 J HH = 4.6 Hz, 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 (101 MHz, C6D6): δ = 142.2 (dd, 2 J CP = 12.5, 2.0 Hz, oTol ipso ), 141.4 (d, 5 J CP = 8.0 Hz, oTol para ), 137.4 (d, 3 J CP= 6.0 Hz, oTol ortho ), 130.7 (d, 4 J CP = 1.5 Hz, oTol meta ), 125.1 (dd, 3 J CP = 5.2 Hz, 4 J CP = 2.5 Hz, oTol ortho’+meta’ ), 67.2 (d, 2 J CP = 5.8 Hz, Mor, C2), 47.4 (d, 3 J CP = 3.8 Hz, Mor, C3), 38.8 (dd, 1 J CP = 15.3 Hz, 3 J CP = 8.0 Hz, Cy, C1), 34.6 (d, 3 J CP = 21.9 Hz, Cy, C3), 30.7 (d, 2 J CP = 7.3 Hz, Cy, C2), 28.9 (d, 3 J CP = 13.8 Hz, Cy, C3), 28.2 (d, 2 J CP = 6.0 Hz, Cy, C2), 27.3 (s, Cy, C4), 22.7 (s, CH3)ppm. 31 P{ 1 H} NMR (162 MHz, C6D6): δ = 48.6 (d, 2 J PP = 161.4 Hz, P(Mor)3), −3.4 (d, 2 J PP= 161.4 Hz, 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°C (decomposition). 32 H 53 Elemental analysis for N3O3P2: Calculated: C 65.17, H 9.06, N 7.13; Found: C 65.14, H 9.19, N 7.06.

[0303] Synthesis of L17:

[0304] [ka]

[0305] Phosphine L17 was synthesized from 17·H2 (1.21 g, 2.39 mmol) according to the general procedure for the P,N-YPhos ligand, except that Cy2PI was added in pentane (20 ml). Excess THF must be present to dissolve the in situ formed ylide. Filtration through a Celite plug was performed in toluene. Colorless crystals suitable for single-crystal X-ray diffraction experiments were obtained by slow evaporation of a saturated hexane solution.

[0306] Yield: (5.67g, 10.4mmol, 87%).

[0307] 1 H NMR (400 MHz, C6D6): δ = 7.28 (d, 3 J HH = 7.8 Hz, 6H, Ph ortho ), 7.11 (t, 3 J HH = 7.9 Hz, 6H, Ph meta ), 6.92 (t, 3 JHH = 7.4 Hz, 3H, Ph para ), 2.74 (d, 3 J HP = 7.8 Hz, 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 (101 MHz, C6D6): δ = 147.9 (d, 2 J CP = 3.1 Hz, Ph ipso ), 128.8 (s, Ph meta ), 127.0 (t, J=2.5Hz, Ph ortho ), 124.5 (s, Ph para ), 40.9 (t, J = 3.9 Hz, CH3NPh), 36.0 (dd, 1 J CP = 14.6, 3 J CP = 9.1 Hz, PCy2, C1), 32.5 (d, 2 J CP = 18.0 Hz, PCy2, C2), 31.8 (d, 2 J CP = 10.8 Hz, PCy2, C2), 28.8 (d, 3 J CP = 7.8 Hz, PCy2, C3), 28.3 (d, 3 J CP = 11.4 Hz, PCy2, C3), 27.5 (s, PCy2, C4), 19.3 (dd, 1 J CP = 202.8, 22.7 Hz, PCPCH3), 15.8 (d, 2 J CP = 12.1 Hz, PCPCH3)ppm. 31 P{ 1 H} NMR (162 MHz, C6D6): δ = 53.4 (d, 2 J PP= 193.3 Hz, P(PhNMe)3), -3.3 (d, 2 J PP = 193.3 Hz, 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 for N3P2: Calculated: C 73.27, H 8.61, N 7.32; Found: C 73.59, H 9.01, N 7.06.

[0308] Synthesis of L18:

[0309] [ka]

[0310] Phosphine L18 was synthesized from 18·H2 (1.30 g, 2.69 mmol) according to the general procedure for the P,N-YPhos ligand.

[0311] Yield: 1.25 g, 2.50 mmol, 54%.

[0312] 1 H NMR (400 MHz, C6D6): δ = 7.49 (d, 3 J HH = 7.7 Hz, 2H, CH ar. ), 7.20 - 7.11 (m, 4H, CH ar. ), 7.07-6.88 (m, 7H, CH ar. ), 3.63 (tt, 3 J HH = 11.2, 5.9 Hz, 2H, CH2, bridge), 2.68 (dh, 2 JHP =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 ar. ), 142.9 (d, J = 8.8 Hz, C ar. ), 138.6 (d, J=2.4 Hz, C ar. ), 134.4 (d, J = 8.0 Hz, C ar. ), 131.0 (s, C ar. ), 129.3 (s, C ar. ), 127.6 (s, C ar. ), 126.63 (s, C ar. ), 126.43 (s, C ar. ), 124.07 (d, J = 1.8 Hz, C ar. ), 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℃.

[0313] General procedure for the palladium-catalyzed Buchwald-Hartwig amination of aryl chlorides: A 5 ml screw-cap vial with a Teflon-coated stir bar and septum cap was charged with 172 mg (1.5 mmol, 1 equiv.) of potassium tert-butoxide inside a glove box. The vial was placed outside the glove box, and 4 ml of tetrahydrofuran, 0.118 ml (1 mmol, 1 equiv.) of 4-chlorotoluene, 0.259 ml of tetradecane (1 mmol, 1 equiv.), and 1.1 mmol (1.1 equiv.) of amine were added via syringe. A second vial was charged with equimolar amounts of the free ligand and tris(dibenzylideneacetone)dipalladium(0). The catalyst was preformed in 0.5 ml of THF and stirred for 30 minutes. The catalyst solution was added to the reaction mixture and stirred at room temperature or 60°C. A small aliquot was removed, filtered through silica with ethyl acetate and analyzed by GC / MS and GC / FID.

[0314] General procedure for coupling of 4-chloroanisole with n-BuLi and t-BuLi: The reaction was carried out in a 5 ml screw-cap vial equipped with a Teflon-coated stir bar and septum cap. Inside the glove box, the palladium source (0.03 mmol) and ligand (0.03 mmol) were added to the vial. The vial was then removed from the glove box, and 4-chloroanisole (1 mmol, 142.6 mg) was added, followed by toluene (1 ml) and stirring for 30 minutes. n-BuLi (1.6 M in hexane, 1.2 mmol, 0.75 ml) was diluted with toluene to a final volume of 3.3 ml and added over 1 hour at room temperature using a syringe pump. The reaction was quenched by adding 0.1 ml of water. A small aliquot was removed, filtered through silica with ethyl acetate, and analyzed by GC / MS and GC / FID.

[0315] General procedure for coupling of 4-chlorotoluene with acetone: A 5 ml screw-cap vial equipped with a Teflon-coated stir bar and septum cap was loaded into a glove box equipped with a base. The vial was placed outside the glove box, and acetone, aryl chloride (1 mmol, 1 equiv.), and 0.259 ml of tetradecane (1 mmol, 1 equiv.) were added via syringe. A second vial was charged with an equimolar amount of free ligand and a palladium source. The catalyst was preformed in 0.5 ml of THF and stirred for 15 minutes. The catalyst solution was added to the reaction mixture and stirred at room temperature for 16 hours. A small aliquot was removed, filtered through silica with ethyl acetate, and analyzed by GC / MS and GC / FID.

[0316] General procedure for gold-catalyzed hydroamination: A 2 mL screw-cap vial equipped with a Teflon-coated stir bar and septum cap was filled with 0.005 mmol L AuCl and NaBAr F The vial was heated to the indicated temperature on a hot plate with stirring. A small aliquot was removed via syringe and added directly to an NMR tube to monitor the progress of the reaction. The yield was 1 It was calculated by integrating the peaks of the alkyne starting material over those of the imine product in the H-NMR spectrum.

[0317] General procedure for hydrogenation of aryl chlorides: 0.03 mmol of Pd2(dba)3 was weighed into a Schlenk tube and 2 mL of THF was added. Then, 0.03 mmol of the ligand was added, and the reaction was allowed to proceed for 30 minutes to produce the active catalyst. 1 mmol each of the halo compound and internal standard was added to the reaction mixture and stirred for an additional 2 hours. Finally, 0.05 mmol of sodium tetrafluoroborate and 1 mmol of potassium phosphate were added, and the reaction vessel was degassed by three freeze-pump-thaw cycles. After the third freeze-pump-thaw cycle, hydrogen was introduced into the reaction mixture, and the Schlenk tube was warmed to 23 °C. The tube was then sealed, and the reaction mixture was vigorously stirred at 50 °C. After 24 hours, the reaction mixture was opened to the air, diluted with ethyl acetate (3 mL), and an aliquot was analyzed by GC or GCMS analysis.

[0318] General procedure for coupling of 4-chlorotoluene with ammonia: The reaction was carried out in a screw-cap vial with a septum cap. Inside the glove box, Pd2dba3 (0.0125 mmol Pd) and the ligand (0.0125 mmol) were added to the vial. THF (0.5 mL) was then added, and the mixture was stirred for 30 minutes. Another vial was charged with KOtBu (57.3 mg, 0.5 mmol), and 4-chlorotoluene (31.6 mg, 29.6 μL, 0.25 mmol), tetradecane (49.6 mg, 6.47 μL, 0.25 mmol), and 1,4-dioxane (2.5 mL) were then added via syringe outside the glove box. The catalyst stock solution was added to the vial, followed by ammonia in dioxane (0.5 M, 2 mL, 1 mmol), and the mixture was heated to 110 °C for 5 hours in a temperature-controlled aluminum heating block. A small aliquot was removed, filtered through silica using ethyl acetate as eluent and analyzed by GC-FID.

[0319] Table 1: Results of the Buchwald-Hartwig amination reaction:

[0320] [ka]

[0321] Conditions A: 1 mmol of ArCl, 1.1 equivalents of amine, 1.5 equivalents of KO t Bu, 0.5 mol% Pd and ligand, room temperature, THF; Condition B: 1 mmol ArCl, 1.1 equiv., amine, 1.5 equiv., KO t Bu, 1 mol% Pd and ligand, room temperature, THF; Condition C: 1 mmol ArCl, 1.1 equiv., amine, 1.5 equiv., KO t Bu, 0.5 mol% Pd and ligand, 50°C, THF.

[0322] Consequences of arylation of ammonia reactions

[0323] [Table 2]

[0324] Ligand screening results for the monoarylation of ammonia (1 mmol) with 4-chlorotoluene (0.25 mmol) using K₃tBu (0.5 mmol), L⋅Pd₂dba₃ (5 mol%) in 1,4-dioxane at 110 °C. Yields are GC-FID yields after 5 h using n-tetradecane as the internal standard and are normalized to the sum of all peaks.

[0325] [Table 3]

[0326] Coupling results of organolithium reagents with aryl chlorides.

[0327] [ka]

[0328] [Table 4]

[0329] Reaction conditions: 1 mmol ArCl, 1.1 equivalents RLi in toluene at room temperature. Addition of R-Li over 1 hour. Yield determined by calibrated GC analysis using tetradecane as internal standard. a) Only isomerized products were observed.

[0330] Acetone allylation reaction results: Table 3: Screening of reaction conditions

[0331] [ka]

[0332] [Table 5]

[0333] Reaction conditions: 1 mmol ArCl, room temperature, 16 h. Yield determined by calibrated GC analysis using tetradecane as internal standard. a) No catalyst preparation, b) Preformation in THF with ArCl for 15 min, c) Preformed in THF with ArCl for 1 hour d) Preformation in ArCl-free THF for 15 min, e) Preformed in THF without ArCl, f) Reacts in wet, technical grade acetone, and air.

[0334] Scope:

[0335] [ka]

[0336] Reaction conditions: 1 mmol ArCl, 3 eq Cs2CO3 in 3.7 ml acetone, 0.1 mol% [Pd(allyl)Cl]2, 0.2 mol% L7, room temperature, 16 h, yield of isolated product.

[0337] The hydrogenation reaction of aryl halides results in:

[0338] [ka]

[0339] [Table 6]

[0340] Reaction conditions: 1 mmol ArCl, 3 mol% Pd2dba3, 3 mol% L, 15 mol% NaBF4, 1 mmol K3PO4 in THF under 1 atm H2 at 50 or 60 °C.

[0341] Synthesis and characterization of products from acetone arylation:

[0342] 1-(4-(tert-butyl)phenyl)propan-2-one (1)

[0343] [ka]

[0344] Compound 1 was synthesized according to the general procedure, purified by filtration on silica, and isolated as a colorless liquid in 99% yield. Analytical data are consistent with reported literature.

[0345] 1 H NMR (400 MHz, CDCl3): δ 7.36 (d, J = 8.27 Hz, 2H), 7.14 (d, J = 8.29 Hz, 2H), 3.66 (s, 2H), 2.16 (s, 3H), 1.32 (s, 9H). 13 C NMR (101 MHz, 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).

[0346] 1-(naphthalen-1-yl)propan-2-one(2)

[0347] [ka]

[0348] Compound 2 was synthesized according to the general procedure, purified by filtration on silica, and isolated as a colorless liquid in 95% yield. Analytical data are consistent with reported literature.

[0349] 1 H NMR (400 MHz, CDCl3): δ 7.88 (ddd, J = 6.94, 4.73, 1.99 Hz, 2H), 7.81 (d, J = 8.13 Hz, 1H), 7.52 (ddd, J = 7.21, 4.93, 1.79 Hz, 2H), 7.47 - 7.42 (m, 1H), 7.41 - 7.36 (m, 1H), 4.12 (s, 2H), 2.12 (s, 3H). 13 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+]).

[0350] Ethyl 2-(2-oxopropyl)benzoate (3)

[0351] [ka]

[0352] Compound 3 was synthesized according to the general procedure and purified by column chromatography (hexane / ethyl acetate 20:1) and isolated as a colorless liquid in 91% yield. Analytical data are consistent with reported literature. 1 H NMR (400 MHz, CDCl3): δ = 7.9 (ddd, J = 6.9, 4.7, 2.0 Hz, 2H), 7.8 (d, J = 8.1 Hz, 1H), 7.5 (ddd, J = 7.2, 4.9, 1.8 Hz, 2H), 7.5 - 7.4 (m, 1H), 7.4 - 7.4 (m, 1H), 4.1 (s, 2H), 2.1 (s, 3H). 13 C NMR (101 MHz, 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), 118.0 (26.5), 135.0 (28.79), 136.0 (62.39), 161.0 (25.21), 164.1 (100, [M+]).

[0353] 1-(4-fluorophenyl)propan-2-one (4)

[0354] [ka]

[0355] Compound 4 was synthesized according to the general procedure, purified by filtration on silica, and isolated as a colorless liquid in 98% yield. Analytical data are consistent with reported literature.

[0356] 1 H NMR (400 MHz. CDCl3): δ 7.16 (dd. J = 8.48. 5.45 Hz. 2H). 7.02 (t. J = 8.64 Hz. 2H). 3.68 (s. 2H). 2.16 (s. 3H). 19 F NMR (75 MHz. 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+]).

[0357] 1-(2-fluorophenyl)propan-2-one (5)

[0358] [ka]

[0359] Compound 5 was synthesized according to the general procedure and purified by column chromatography (hexane / ethyl acetate 20:1) and isolated as a colorless liquid in 85% yield. Analytical data are consistent with reported literature. 1 H NMR (400 MHz. CDCl3): δ 7.30 - 7.23 (m. 1H). 7.18 (td. J = 7.48. 1.89 Hz. 1H). 7.14 - 7.03 (m. 2H). 3.74 (s. 2H). 2.20 (s. 3H). 13 C NMR (101 MHz. CDCl3) δ 205.1. 161.1 (d. J = 245.71 Hz). 131.8 (d. J = 4.21 Hz). 129.2 (d. J = 8.11 Hz). 124.4 (d. J = 3.62 Hz). 121.8 (d. J = 16.19 Hz). 115.6 (d. J = 21.71 Hz). 44.0 (d. J = 2.31 Hz). 29.5. 19 F NMR (75 MHz. 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). 1252 (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+]).

[0360] 1-(3-(methylthio)phenyl)propan-2-one (6)

[0361] [ka]

[0362] Compound 6 was synthesized according to the general procedure and purified by column chromatography (hexane / ethyl acetate 20:1) and isolated as a colorless liquid in 93% yield. Analytical data are consistent with reported literature. 1 H NMR (400 MHz. CDCl3): δ 7.25 (t. J = 7.69 Hz. 1H). 7.16 (dt. J = 8.16. 1.47 Hz. 1H). 7.09 (d. J = 1.83 Hz. 1H). 6.97 (dt. J = 7.58. 1.40 Hz. 1H). 3.66 (s. 2H). 2.48 (s. 2H). 2.16 (s. 3H). 13 C NMR (101 MHz. 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+]).

[0363] 1-chloro-2-methylbenzene(7)

[0364] [ka]

[0365] Compound 7 was synthesized according to the general procedure and purified by column chromatography (hexane / ethyl acetate 20:1) and isolated as a colorless liquid in 73% yield. Analytical data are consistent with reported literature. 1 H NMR (400 MHz. CDCl3) δ 7.22- 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 (101 MHz. 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). (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+]).

[0366] 1-(5-methoxy-2-methylphenyl)propan-2-one (8)

[0367] [ka]

[0368] Compound 8 was synthesized according to the general procedure and purified by column chromatography (hexane / ethyl acetate 20:1) and isolated as a colorless liquid in 60% yield. Analytical data are consistent with reported literature. 1 H NMR (400 MHz. 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+]).

[0369] 1-(1-methyl-1H-pyrrolo[2.3-b]pyridin-4-yl)propan-2-one (9)

[0370] [ka]

[0371] Compound 9 was synthesized according to the general procedure and purified by column chromatography (hexane / ethyl acetate 20:1) and isolated as a colorless liquid in 78% yield. 1 H NMR (400 MHz. CDCl3): δ 8.30 (d. J = 4.84 Hz. 1H). 7.19 (d. J = 3.46 Hz. 1H). 6.92 (d. J = 4.83 Hz. 1H). 6.44 (d. J = 3.44 Hz. 1H). 3.94 (s. 2H). 3.89 (s. 3H). 2.14 (s. 3H). 13 C NMR (101 MHz. CDCl3): δ 205.1. 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). 1087 (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 NO [M+H] + Calculated: 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+]).

[0372] 1-(3,5-dimethoxyphenyl)propan-2-one (10)

[0373] [ka]

[0374] Compound 10 was synthesized according to the general procedure and purified by column chromatography (hexane / ethyl acetate 20:1) and isolated as a colorless liquid in 97% yield. Analytical data are consistent with reported literature. 1 H NMR (400 MHz. CDCl3): δ 6.37 (t. J = 2.23 Hz. 3H). 6.35 (d. J = 2.25 Hz. 6H). 3.78 (s. 5H). 3.61 (s. 2H). 2.15 (s. 3H). 13 C NMR (101 MHz. 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). 1293 (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+]).

[0375] 1-(3-methylbenzo[b]thiophen-5-yl)propan-2-one (11)

[0376] [ka]

[0377] Compound 11 was synthesized according to the general procedure and purified by column chromatography (hexane / ethyl acetate 20:1) and isolated as a colorless liquid in 97% yield. 1H NMR (400 MHz. CDCl3): δ 7.81 (d. J = 8.20 Hz. 1H). 7.67 - 7.38 (m. 1H). 7.19 (dd. J = 8.29. 1.69 Hz. 1H). 7.09 (d. J = 1.41 Hz. 1H). 3.84 (s. 2H). 2.43 (d. J = 1.24 Hz. 3H). 2.18 (s. 3H). 13 C NMR (101 MHz. CDCl3): δ 206.8. 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). 1090 (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 / zC 12 H 13 OS [M+H] + Calculated value: 205.0687, Measured value: 205.0679 MS (EI): m / z (%)= 115.0 (14.3), 128.0 (9.61), 161.1 (100), 162.0 (16.09), 204.0 (30,0 [M+]).

[0378] 1-(benzo[d][1.3]dioxol-5-yl)propan-2-one (12)

[0379] [ka]

[0380] Compound 12 was synthesized according to the general procedure and purified by column chromatography (hexane / ethyl acetate 20:1) and isolated as a colorless liquid in 76% yield. Analytical data are consistent with reported literature. 1 H NMR (400 MHz. CDCl): δ = 6.7 (d. J = 7.82 Hz. 1H). 6.7 (d. J = 1.73 Hz. 1H). 6.6 (dd. J = 7.91. 1.73 Hz. 1H). 5.9 (s. 2H). 3.6 (s. 2H). 2.1 (s. 3H). 13 C NMR (101 MHz. 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). 1187 (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+]).

[0381] 2-Methyl-1H-indole (13)

[0382] [ka]

[0383] Compound 13 was synthesized according to the general procedure and purified by column chromatography (hexane / ethyl acetate 20:1) and isolated as a colorless liquid in 71% yield. Analytical data are consistent with reported literature. 1H NMR (400 MHz. CDCl3): δ = 7.6 - 7.3 (m. 1H). 7.2 (dd. J = 14.67. 7.20 Hz. 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). 1284 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+]).

[0384] (4-chlorophenyl)trimethylsilane (14)

[0385] [ka]

[0386] Compound 14 was synthesized according to the general procedure and purified by column chromatography (hexane / ethyl acetate 20:1) and isolated as a colorless liquid in 92% yield. 1 H NMR (400 MHz. CDCl3): δ = 7.50 (d. J = 7.82 Hz. 2H). 7.20 (d. J = 7.64 Hz. 2H). 3.70 (s. 2H). 2.17 (s. 3H). 0.27 (s. 9H). 13 C NMR (101 MHz. CDCl3): δ = 206.4. 139.1 134.8 133.9 128.9 51.1 29.4 -1.029 SiNMR (80 MHz. 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). 1247 (m). (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+]).

[0387] 1-(4-benzoylphenyl)propan-2-one (15)

[0388] [ka]

[0389] Compound 15 was synthesized according to the general procedure and purified by column chromatography (hexane / ethyl acetate 20:1) and isolated as a colorless liquid in 71% yield. Analytical data are consistent with reported literature. 1 H NMR (400 MHz. CDCl3): δ = 7.82 - 7.77 (m. 3H). 7.75 (d. J = 8.23 ​​Hz. 1H). 7.62 - 7.55 (m. 1H). 7.48 (td. J = 7.43. 3.56 Hz. 2H). 7.31 (dd. J = 8.14. 3.87 Hz. 1H). 7.23 (d. J = 8.24 Hz. 1H). 2.63 (s. 2H). 2.17 (s. 3H). 13C NMR (101 MHz. 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). 1178 (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+]).

[0390] 1-(4-vinylphenyl)propan-2-one (16)

[0391] [ka]

[0392] Compound 16 was synthesized according to the general procedure and purified by column chromatography (hexane / ethyl acetate 20:1) and isolated as a colorless liquid in 90% yield. Analytical data are consistent with reported literature. 1 H NMR (400 MHz. CDCl3): δ = 7.38 (d. J = 8.2 Hz. 1H). 7.17 (d. J = 8.1 Hz. 1H). 6.70 (dd. J = 17.6. 10.9 Hz. 1H). 5.74 (d. J = 17.6 Hz. 1H). 5.24 (d. J = 10.9 Hz. 1H). 3.68 (s. 1H). 2.15 (s. 1H). 13C NMR (101 MHz. 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). 1356 (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+]).

[0393] 1-(4-(dimethylamino)phenyl)propan-2-one (17)

[0394] [ka]

[0395] Compound 17 was synthesized according to the general procedure and purified by column chromatography (hexane / ethyl acetate 20:1) and isolated as a colorless liquid in 90% yield. Analytical data are consistent with reported literature. 1 H NMR (400 MHz. CDCl3): δ = 7.07 (d. J = 8.57 Hz. 2H). 6.72 (d. J = 8.30 Hz. 2H). 3.58 (s. 2H). 2.94 (s. 6H). 2.12 (s. 3H). 13 C NMR (101 MHz. CDCl3) δ 203.3. 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+]).

[0396] Preparation of metal complexes

[0397] L1-Pd(dba):

[0398] [ka]

[0399] 32.8 mg (0.058 mmol) of L1 and 39.2 mg (0.058 mmol Pd, 15.6 m% Pd) were suspended in 0.5 mL of THF in a J. Young NMR tube. A dark red solution formed, which was shaken for 1 h. Single crystals of L1-Pd(dba) were obtained by diffusing pentane into the concentrated solution in THF.

[0400] 31 P NMR (162 MHz, THF): δ = 67.1 (d, 2 J PP = 120.4 Hz, P + Pip3), 20.0 (d, 2 J PP =121.3 Hz, PCy2).

[0401] L2-Pd(dba):

[0402] [ka]

[0403] 25 mg (0.049 mmol) of L2 and 33.5 mg (0.049 mmol Pd, 15.6 m% Pd) were suspended in 0.5 mL of THF in a J. Young NMR tube. A dark red solution formed, which was shaken for 1 h. L2-Pd(dba) was obtained as an orange solid with 0.5 equivalents of dba.

[0404] 1 H NMR (400 MHz, THF): δ = 7.74 (d, J = 15.98 Hz, 3H), 7.70 - 7.65 (m, 5H), 7.40 - 7.35 (m, 9H), 7.22 (d, J = 16.01 Hz, 4H), 3.06 (d, J = 12.91 Hz, 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 (162 MHz, THF): δ = 75.6 (d, 2 J PP = 120.8 Hz, P + Pip3), 22.2 (d, 2 J PP = 121.2 Hz, PCy2).

[0405] L1-Pd(o Tol)Br:

[0406] [ka]

[0407] 32.8 mg (0.058 mmol) of L1 and 39.2 mg (0.058 mmol Pd, 15.6 m% Pd) were suspended in 0.5 mL of THF in a J. Young NMR tube. A dark red solution formed, which was shaken for 1 h. 0.1 mL (0.863 mmol, 15 equiv.) of 4-bromotoluene was then added, and the mixture was shaken overnight. Single crystals of L1-Pd(oTol)Br were obtained by diffusing pentane into the concentrated solution in THF.

[0408] 31 P NMR (162 MHz, THF): δ = 71.4 (d, 2 J PP = 103.8 Hz, P + Pip3), 12.5 (d, 2 J PP =103.2 Hz, PCy2).

[0409] L3-Pd(o Tol)Br

[0410] [ka]

[0411] 30.0 mg (0.032 mmol) of L3 and 41.8 mg (0.062 mmol Pd, 15.6 m% Pd) were suspended in 0.5 mL of THF in a J. Young NMR tube. A dark red solution formed, which was shaken for 1 h. 0.15 mL (1.23 mmol, 20 equiv.) of 4-bromotoluene was then added, and the mixture was shaken overnight. Single crystals of L3-Pd(oTol)Br were obtained by diffusing pentane into the concentrated solution in THF.

[0412] 31 P NMR (162 MHz, THF): δ = 72.6 (d, 2 J PP = 64.4 Hz, P + Pip3), 25.6 (d, 2 J PP=64.4 Hz, PCy2).

[0413] L3-Pd(o Tol)Cl:

[0414] [ka]

[0415] 30.0 mg (0.032 mmol) of L3 and 41.8 mg (0.062 mmol Pd, 15.6 m% Pd) were suspended in 0.5 mL of THF in a J. Young NMR tube. A dark red solution formed, which was shaken for 1 h. 0.15 mL (1.23 mmol, 20 equiv.) of 4-chlorotoluene was then added, and the mixture was shaken overnight. Single crystals of L3-Pd(oTol)Cl were obtained by diffusing pentane into the concentrated solution in THF.

[0416] 31 P NMR (162 MHz, THF): δ = 72.6 (d, 2 J PP = 64.4 Hz, P + Pip3), 25.6 (d, 2 J PP =64.4 Hz, PCy2). Isomers:71.4 (d, 2 J PP = 86.7 Hz, P + Pip3), 25.0 (d, 2 J PP =87.2 Hz, PCy2).

[0417] L2-PdCl2:

[0418] [ka]

[0419] 25.0 mg (0.049 mmol) of L2 and 12.8 mg (0.049 mmol, 1 equiv.) of Pd(MeCN)Cl2 were suspended in 0.5 mL of THF in a J. Young NMR tube. After shaking for 1 h, a red solution rapidly formed, during which time L2-PdCl2 precipitated as an orange solid.

[0420] 31 P NMR (162 MHz, THF): δ = 51.4 (d, 2 J PP = 15.3 Hz, P + Pip3), 44.7 (d, 2 J PP =15.1 Hz, PCy2).

[0421] L3-PdCl2:

[0422] [ka]

[0423] 20.0 mg (0.041 mmol) of L3 and 10.7 mg (0.041 mmol, 1 equiv.) of Pd(MeCN)Cl were suspended in 0.5 mL of THF in a J. Young NMR tube. After shaking for 1 h, a red solution rapidly formed, during which time L2-PdCl2 precipitated as an orange solid.

[0424] 31 P NMR (162 MHz, THF): δ = 85.3 (d, 2 J PP = 58.0 Hz, P + Pip3), 47.5 (d, 2 J PP =58.0 Hz, PCy2).

[0425] L7-PdCl2:

[0426] [ka]

[0427] 25.0 mg (0.043 mmol) of L7 and 11.1 mg (0.043 mmol, 1 equiv.) of Pd(MeCN)Cl were suspended in 0.5 mL of THF in a J. Young NMR tube. After shaking for 1 h, a red solution rapidly formed, during which time L7-PdCl precipitated as an orange solid.

[0428] 31 P NMR (162 MHz, THF): δ = 85.3 (d, 2 J PP = 58.1 Hz, P + ), 47.5 (d, 2 J PP = 58.0 Hz, PCy2).

[0429] L1-AuCl:

[0430] [ka]

[0431] 93.3 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 formed, and the solid was filtered, washed with 3 × 3 mL of pentane, and dried in vacuo. L1-AuCl was obtained as a colorless solid in 88% yield (110 mg, 0.137 mmol).

[0432] 1 H NMR (400 MHz, C6D6): δ = 7.29 - 7.23 (m, 2H, Ph orto ), 7.22 - 7.17 (m, 2H, Ph meta ), 7.11 - 7.05 (m, 1H, Ph para ), 3.02 (q, 3 J HP= 5.0 Hz, 12H, Pip Pos.1 CH2), 2.56 - 2.46 (m, 2H, Cy Pos.3, CH2), 1.98 - 1.76 (m, 4H, Cy Pos.1, CH + Cy Pos.2, CH2), 1.66 - 1.52 (m, 4H, Cy Pos.2 + Pos.4, CH2), 1.50 - 1.32 (m, 24H, Pip Pos.2 + Pos.3 CH2;Cy Pos.3, CH2), 1.29 - 1.18 (m, 2H, Cy Pos.4, CH2), 1.17 - 1.05 (m, 4H, Cy Pos.2, CH2). 13 C NMR (101 MHz, C6D6): δ = 141.3 (dd, 2 J CP = 8.6, 2.6 Hz, Ph ypso , C), 136.7 (dd, 3 J CP = 6.0, 2.4 Hz, Ph ortho , CH), 127.9 (s, Ph meta , CH), 125.6 (d, 2 J = 2.5 Hz, CH), 48.2 (s, Pip Pos.1, CH), 41.0 (dd, 1 J CP = 37.9 Hz, 3 J CP = 3.3 Hz, Cy Pos.1, CH), 33.3 (d, 3 J CP = 2.4 Hz, Cy Pos.3, CH2), 31.0 (s, Cy Pos.3, CH2), 29.7 (dd, 1 J CP = 196.7, 60.4 Hz, P-C - -P), 28.2 (d, 2 J CP = 13.6 Hz, Cy Pos.2, CH2), 27.3 (d, 2 J CP = 12.1 Hz, CH2), 26.5 (s, Cy Pos.4, CH2), 26.4 (d, 2 JCP = 5.0 Hz, Pip Pos.2, CH2), 25.0 (s, Pip Pos.3, CH2). 31 P NMR (162 MHz, C6D6): δ = 54.2 (d, 2 J PP = 74.8 Hz, P + Pip3), 31.0 (d, 2 J PP = 75.3 Hz, PCy2).

[0433] L2-AuCl:

[0434] [ka]

[0435] 83.2 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 formed, and the solid was filtered, washed with 3 × 3 mL of pentane, and dried in vacuo. L2-AuCl was obtained as a colorless solid in 86% yield (99 mg, 0.134 mmol).

[0436] 1 H NMR (400 MHz, C6D6): δ = 3.09 (q, 3 J HP = 5.4 Hz, 12H, Pip Pos.1, CH2), 2.06 - 1.91 (m, 6H, Cy Pos. 1 , CH, + Cy Pos.3, CH2), 1.83 - 1.70 (m, 4H, Cy Pos.2 + Pos.3 , CH2), 1.68 - 1.57 (m, 6H, Cy Pos.3 + Pos.4, CH2), 1.54 (dd, 3 J HP= 14.4, 9.9 Hz, 3H, CH3), 1.50 - 1.42 (m, 6H, Pip Pos.3, CH2), 1.39 - 1.29 (m, 12H, Pip Pos.2, CH2), 1.27 - 1.07 (m, 6H, Cy Pos.2 + Pos.3, CH2). 13C NMR (101 MHz, C6D6): δ = 48.0 (s, Pip Pos.1, CH2, 37.8 (dd, 1 J CP = 39.2 Hz, 3 J CP = 4.3 Hz, Cy Pos.1, CH ), 31.7 (d, 3 J CP = 3.9 Hz, Cy Pos.3 , CH2), 30.9 (s, Cy Pos.3, CH2), 27.7 (d, 2 J CP = 11.7 Hz, Cy Pos.2, CH2), 27.3 (d, 2 J CP = 14.0 Hz, Cy Pos.2, CH2), 26.7 (s, Pip Pos.2, CH2), 26.7 (s, Cy Pos.4, CH2), 25.0 (s, Pip Pos.3, CH2), 16.4 (dd, 3 J CP = 6.1, 1.8 Hz, CH3), 7.2 (dd, 1 J CP = 196.9, 71.0 Hz, P-C - -P). 31 P NMR (162 MHz, C6D6): δ = 62.4 (d, 2 J PP = 83.0 Hz, P + Pip3), 35.9 (d, 2 J PP = 83.1 Hz, PCy2).

[0437] L5-AuCl:

[0438]

Chem.

[0439] 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 formed, and the solid was filtered, washed with 3 × 3 mL of pentane, and dried in vacuo. L5-AuCl was obtained as a colorless solid in 54% yield (65 mg, 0.085 mmol).

[0440] 1 H NMR (400 MHz, C6D6): δ = 3.05 (q, 3 J = 5.3 Hz, 12H, Pip Pos.1, CH2), 2.52 - 2.33 (m, 3H, iPr, CH, Cy Pos.3, CH2), 2.11 - 1.98 (m, 4H, Cy Pos.1, CH , Cy Pos.3, CH2), 1.85 - 1.69 (m, 4H, Cy Pos.2, CH2), 1.66 - 1.54 (m, 4H, Cy Pos.2 + Pos.3, CH2), 1.51 - 1.31 (m, 20H, Pip Pos. 2 + Pos.3 + Cy Pos.3, CH2), 1.29 - 1.08 (m, 12H, iPr CH3, Cy Pos.2 + Pos.4, CH2). 13 C NMR (101 MHz, C6D6): δ = 48.6 (s, Pip Pos.1, CH2), 41.8 (d, 1 J CP = 35.6 Hz, Cy Pos.1, CH), 34.7 (s, Cy Pos.3, CH2) , 32.6 (s, Cy Pos.3, CH2, 30.5 (d, 2 J CP = 11.4 Hz, iPr CH(CH3)2, 28.3 (d, 2 J CP = 13.7 Hz, Cy Pos.2, CH2), 27.9 (d, 2 J CP= 12.2 Hz, Cy Pos.2, CH2), 26.8 (d, 3 J CP = 4.8 Hz, iPr, CH(CH3)2), 26.6 (d, 3 J = 1.6 Hz, Cy Pos.4, CH2), 26.5 (d, 3 J CP = 4.6 Hz, Pip Pos.2, CH2), 25.1 (s, Pip Pos.3). 31 P NMR (162 MHz, C6D6): δ = 61.5 (d, 2 J PP = 82.1 Hz, P + Pip3), 39.3 - 38.5 (d br, 2 J PP = 82.1 Hz, PCy2).

[0441] L6-AuCl:

[0442] [ka]

[0443] 74.6 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 formed, and the solid was filtered, washed with 3 × 3 mL of pentane, and dried in vacuo. L6-AuCl was obtained as a colorless solid in 81% yield (87 mg, 0.085 mmol).

[0444] 1 H NMR (400 MHz, C6D6): δ = 3.11 (q, 3 J = 5.8 Hz, 12H, Pip Pos.1, CH2), 1.60 (dd, 3 J HP = 14.8, 9.5 Hz, 3H CH3), 1.51 (m, 6H, Pip Pos.3 CH2), 1.35 (d, 3 J HP= 14.1 Hz, 18H, t Bu, CH3), 1.31 - 1.23 (m, 12H, Pip Pos.2 CH2). 13 C NMR (101 MHz, C6D6): δ = 47.8 (s, Pip Pos.1, CH2), 40.9 (dd, 1 J CP = 31.7 Hz, 3 J CP = 5.7 Hz, t Bu C(CH3)3), 31.9 (d, 2 J CP = 5.9 Hz, t Bu C(CH3)3), 26.9 (d, 3 J CP = 4.4 Hz, Pip Pos.2, CH2), 24.9 (s, Pip Pos.3, CH2), 18.4 (dd, 2 J CP = 4.9, 2.0 Hz, CH3), 12.4 (dd, 1 J CP = 197.3, 70.8 Hz, P-C - -P). 31 P NMR (162 MHz, C6D6): δ = 60.7 (d, 2 J PP = 87.1 Hz, P + Pip3), 58.3 (d, 2 J PP = 87.1 Hz, PCy2).

[0445] L3-AuCl:

[0446]

Chem.

[0447] 79.7 mg (0.164 mmol) of L3 and 50.0 mg of Au(tht)Cl (0.164 mmol) were suspended in 4 mL of pentane and stirred overnight. A colorless suspension formed, and the solid was filtered, washed with 3 × 3 mL of pentane, and dried in vacuo. L3-AuCl was obtained as a colorless solid in 71% yield (80 mg, 0.111 mmol).

[0448] 1 H NMR (400 MHz, C6D6): δ = 7.21 - 7.16 (m, 2H, Ph ortho , CH2), 7.13 - 7.06 (m, 2H, Ph meta , CH2), 7.05 - 6.98 (m, 1H, Ph para , CH2), 3.85 (s, 2H, N(CH2)2N), 2.68 (dq, 3 J = 8.6, 5.3 Hz, 2H, N(CH2)2N), 2.42 (d, 3 J HP = 9.2 Hz, 6H, NCH3), 2.01 (s, 3H, PCy Pos.1, CH + PCy2Pos.3, CH2), 1.91 - 1.80 (m, 2H, PCy2Pos.1, CH), 1.74 (d, 3 J = 12.7 Hz, 2H, PCy2Pos.3, CH2), 1.69 - 1.61 (m, 4H, PCy Pos.2 + PCy2Pos.2, CH2), 1.59 - 1.48 (m, 4H, PCy Pos.4 + PCy2Pos.3, CH2), 1.46 - 1.33 (m, 3H, PCy2Pos.4 + Pos.2, CH2), 1.32 - 1.18 (m, 4H, PCy2Pos.2, CH2), 1.15 - 1.00 (m, 7H, PCy2Pos.2 + Pos.3, CH2), 0.84 - 0.55 (m, 4H, PCy2Pos.2 + Pos.4, CH2). 13 C NMR (101 MHz, C6D6): δ = 140.5 (dd, 2 J CP= 14.0, 2.9 Hz, Ph ypso , C), 136.2 (s, Ph ortho , CH), 127.8 (s, Ph meta , CH), 125.6 (s, Ph para , CH), 47.3 (d, 2 J = 6.8 Hz, N(CH2)2N), 39.2 (dd, 1 J PCP = 85.1 Hz, 3 J CP = 5.4 Hz, PCy Pos.1, CH), 37.5 (d, 1 J CP = 38.7 Hz, PCy2, CH), 32.9 (d, 2 J CP = 7.0 Hz, N(CH3)), 30.4 (d, 3 J CP = 2.4 Hz, PCy2Pos.3, CH2), 29.9 (s, PCy2Pos.3, CH2), 28.2 (dd, 1 J CP = 114.4, 90.4 Hz, P-C - -P), 27.2 (d, 2 J CP = 12.1 Hz, PCy Pos.2, CH2), 26.8 (d, 2 J CP = 13.6 Hz, PCy2Pos.2, CH2), 26.5 (d, 2 J CP = 13.6 Hz, PCy2Pos.3, CH2), 26.2 (s, PCy Pos.3, CH2), 25.9 (s, PCy2Pos.4, CH2), 22.4 (s, PCy Pos.4, CH2). 31 P NMR (162 MHz, C6D6): δ = 61.3 (d, 2 J PP = 53.1 Hz, P + ), 26.3 (d, 2 J PP = 52.5 Hz, PCy2).

[0449] L10-AuCl:

[0450] [ka]

[0451] 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%).

[0452] 1 H NMR (400 MHz, CD2Cl2): δ = 7.30 (d, 3 J HH = 7.2 Hz, 1H, oTol ortho ), 7.20 (d, 3 J HH = 7.3 Hz, 1H, oTol meta ), 7.15 - 7.02 (m, 2H, oTol meta’+para ), 3.69 - 3.49 (m, 2H, NC2H4N), 3.14 - 3.02 (m, 2H, NC2H4N), 2.77 (dd, 3 J HP = 28.2 Hz, 5 J CP = 9.1 Hz, 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 (101 MHz, CD2Cl2): δ = 141.8 (dd, 2 J CP = 5.6, 3.3 Hz, oTol ipso ), 139.4 (dd, 3 J CP= 4.9, 2.2 Hz, oTol ortho ), 139.1 (dd, 3 J CP = 12.9, 3.0 Hz, oTol ortho’ ), 131.4 (t, 4 J CP = 2.0 Hz, oTol meta ), 126.9 (t, 4 J CP = 2.4 Hz, oTol meta’ ), 125.9 (t, 5 J CP = 2.2 Hz, oTol para ), 48.3 to 48.0 (m, NC2H4N), 41.5 (dd, 1 J CP =85.7Hz, 3 J CP = 5.8 Hz, Cy, C1), 40.4 (dd, 1 J CP = 38.7 Hz, 3 J CP = 5.2 Hz, PCy2, C1), 37.24 (dd, 1 J CP =37.4 Hz, 3 J CP = 1.6 Hz, PCy2, C1), 34.6 (d, 2 J CP = 7.0 Hz;NCH3), 34.0 (d, 2 J CP = 6.6 Hz, NCH3), 32.4 (d, 2 J CP = 2.6 Hz, Cy, C2), 31.7 (s, Cy, C2), 30.8 (d, 3 J CP = 1.8 Hz, Cy, C3), 28.7 (d, 3 J CP = 4.2 Hz, PCy2, C3), 27.9 (dd, 2 J CP = 12.9 Hz, 4 J CP = 9.5 Hz, PCy2, C2), 27.5 (dd,2 J CP = 13.1 Hz, 2 J CP = 4.8 Hz, 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 (162 MHz, CD2Cl2): δ = 59.2 (d, 2 J PP = 54.1 Hz, PCy(MeNC2H4NMe)), 31.0 (d, 2 J PP =54.1 Hz, 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°C (decomposition). 30 H 50 Elemental analysis for AuClN2P2: Calculated: C49.15, H6.87, N3.82; Found: C48.80, H6.87, N3.78.

[0453] L11-AuCl:

[0454] [ka]

[0455] 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%).

[0456] 1H NMR (400 MHz, CD2Cl2): δ = 7.33 (d, 3 J HH = 7.5 Hz, 1H, oTol ortho ), 7.20 (d, 3 J HH = 7.4 Hz, 1H, oTol meta ), 7.15 - 7.01 (m, 2H, oTol meta’+para ), 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. 13 C{ 1 H} NMR (101 MHz, CD2Cl2): δ = 142.5 (dd, 2 J CP = 7.1, 3.1 Hz, oTol ipso ), 139.4 - 139.3 (m, oTol ortho ), 139.2 (d, 3 J CP = 3.2 Hz, oTol ortho’ ), 131.5 (t, 4 J CP = 1.8 Hz, oTol meta ), 126.9 (t, 4 J CP = 2.3 Hz, oTol meta’ ), 126.0 (t, 5 J CP = 2.2 Hz, oTol para ), 44.2 (dd, 2 J CP = 24.9 Hz, 2 J CP = 8.4 Hz, NCH(CH3)2), 43.1 (dd, 1 J CP = 82.6 Hz,3 J CP = 5.9 Hz, Cy, C1), 41.1 to 40.4 (m, PCy2, C1), 37.5 (dd, 2 J 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 to 27.3 (m, Cy / PCy2), 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. PCP is the most common form of PCP. 31 P{ 1 H} NMR (162 MHz, CD2Cl2): δ = 58.9 (d, 2 J PP= 57.0Hz, 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: C 51.74, H 7.41, N 3.55; Found: C 52.08, H 7.58, N 3.55.

[0457] L12-AuCl:

[0458] [ka]

[0459] 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%).

[0460] 1 H NMR (400 MHz, CD2Cl2): δ = 7.28 (d, 3 J HH = 7.5 Hz, 1H, oTol ortho ), 7.21 (d, 3 J HH = 7.3 Hz, 1H, oTol meta ), 7.13 - 7.03 (m, 2H, oTol meta’+para), 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, 4.2 Hz, 12H, CH3, iPen), 0.92 - 0.59 (m, 3H, Cy / PCy2)ppm. 13 C{ 1 H} NMR (101 MHz, CD2Cl2): δ = 142.0 (dd, 2 J CP = 5.8, 3.2 Hz, oTol ipso ), 139.2 (d, 3 J CP = 3.0 Hz, oTol ortho ), 139.1 (d, 3 J CP = 3.0 Hz, oTol ortho’ ), 131.5 (d, 4 J CP = 1.9 Hz, oTol meta ), 126.9 (d, 4 J CP = 2.8 Hz, oTol meta’ ), 126.1 (s, oTol para ), 46.4 (t, J = 6.1 Hz, NCH2), 45.5 (dd, 2 J CP = 18.7 Hz, 4 J CP = 6.8 Hz, NC2H4N), 41.9 (dd, 1 J CP = 41.9 Hz, 3 J CP= 5.4 Hz, Cy, C1), 41.3 (t, J = 5.5 Hz, PCy2, C1), 38.7 - 38.2 (m, CH2, iPen+PCy2, C1), 33.7 (dd, J CP = 6.4, 3.1 Hz, Cy / PCy2), 30.6 (d, 2 J CP = 21.2 Hz, Cy, C2), 28.22 - 26.62 (m, Cy / PCy2), 23.2 (d, 5 J CP = 4.1 Hz, 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 (162 MHz, CD2Cl2): δ = 60.9 (d, 2 J PP = 55.8 Hz, PCy(iPenNC2H4NiPen)), 31.3 (d, 2 J PP =55.8 Hz, 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°C (decomposition). 38 H 66 Elemental analysis for AuClN2P2: Calculated: C 53.99, H 7.87, N 3.31; Found: C 53.68, H 8.11, N 3.25.

[0461] L13-AuCl:

[0462] [ka]

[0463] 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%).

[0464] 1 H NMR and 13 C{ 1 {H}NMR could not be assessed due to the existence of two different conformations in solution. Decomposition of the complex is observed during high-temperature NMR spectroscopy. 31 P{ 1 H} NMR (162 MHz, CD2Cl2): δ = 81.0 (d, 2 J PP = 75.6 Hz, PCy(neoPenNC2H4NneoPen)), 78.1 (d, 2 J PP = 50.0 Hz, PCy(neoPenNC2H4NneoPen)), 36.9 (d, 2 J PP = 75.6 Hz, PCy2), 34.8 (d, 2 J PP = 50.0 Hz, 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°C (decomposition). 32 H 62 Elemental analysis for AuClN2P2: Calculated: C 49.97, H 8.12, N 3.64; Found: C 49.77, H 8.14, N 3.55.

[0465] L14-AuCl:

[0466] [ka]

[0467] 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%).

[0468] 1 H NMR (400 MHz, CD2Cl2): δ = 6.86 (d, 5 J HP = 2.5 Hz, 4H, Mes meta ), 4.29 - 4.16 (m, 1H, Cy, H1), 3.7 (s, 2H, NC2H4N), 3.6 (s, 2H, NC2H4N'), 2.50 (d, 5 J HP = 3.9 Hz, 12H, CH3, Mes ortho ), 2.22 (s, 8H, CH3, Mes para +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, 10.6 Hz, 3H, PCPCH3), 1.37 - 1.13 (m, 4H, Cy, H2+3), 1.07 (dd, 3 J HP = 16.9, 3 J HH = 7.0 Hz, 6H, CH3, iPr), 0.75 (dd, 3 J HP = 16.9, 3 J HH = 7.1 Hz, 6H, CH3, iPr')ppm. 13 C{ 1 H} NMR (101 MHz, CD2Cl2): δ = 139.2 (d, 2 J CP = 5.0 Hz, Mes ipso), 137.3 (s, Month ortho ), 137.0 (s, Month ortho’ ), 136.2 (d, 5 J CP = 1.3 Hz, Mes para ), 131.2 (s, Month meta ), 131.0 (s, Month meta’ ), 51.0 (d, 2 J CP = 8.8Hz, NC2H4N), 40.8 (dd, 1 J CP = 85.4 Hz, 3 J CP = 2.3 Hz, Cy, C1), 29.4 (s, Cy, C2+ CH(CH3)2), 26.8 (d, 4 J CP =1.9 Hz, Cy, C4), 26.4 (d, 3 J CP = 14.7 Hz, Cy, C3), 21.6 (s, CH3, Mes ortho ), 20.9 - 20.8 (m, CH3, iPr), 20.8 (s, CH3, Mes para ), 17.6 (dd, 1 J CP = 141.8, 64.3 Hz, PCP), 15.7 (d, 2 J CP = 1.7 Hz, PCPCH3)ppm. 31 P{ 1 H} NMR (162 MHz, CD2Cl2): δ = 58.1 (d, 2 J PP = 74.1 Hz, PiPr2), 47.9 (d, 2 J PP= 74.1 Hz, 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°C (decomposition). 34 H 54 Elemental analysis for AuClN2P2: Calculated: C 52.01, H 6.93, N 3.57; Found: C 51.71, H 7.02, N 3.32.

[0469] L15-AuCl:

[0470] [ka]

[0471] 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%).

[0472] 1 H NMR and 13 C{ 1 {H}NMR could not be assessed due to the existence of two different conformations in solution. Decomposition of the complex is observed during high-temperature NMR spectroscopy. 31 P{ 1 H} NMR (162 MHz, CD2Cl2): δ = 60.8 (d, 2 J PP = 53.2 Hz), 59.6 (d, 2 J PP = 51.2 Hz), 31.9 (d, 2 J PP =53.2 Hz, PCy2), 31.2 (d, 2 J PP= 51.2 Hz, PCy2)ppm. IR (ATR): 293 (m), 2848 (m), 1442 (w), 1212 (m), 1178 (m), 1012 (s), 922 (m), 890 (m), 847 (w), 807 (w), 759 (w), 730 (m), 552 (m), 523 (m), 482 (m), 424 (m)cm -1 Melting point: 223°C (decomposition). 34 H 56 Elemental analysis for AuClN2P2: Calculated: C 51.88, H 7.17, N 3.56; Found: C 51.85, H 7.12, N 3.51.

[0473] L16-AuCl:

[0474] [ka]

[0475] 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 overnight at room temperature. The solution was overlaid with pentane (15 mL) and left overnight. A colorless solid precipitated from the solution. The solid was filtered and washed with pentane (3 × 5 mL). The gold complex L7AuCl was obtained as a colorless solid after drying in vacuo at 50 °C. 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: (85.0 mg, 0.103 mmol, 66%).

[0476] 1 H NMR (400 MHz, CD2Cl2): δ = 7.27 - 7.20 (m, 2H, oTol ortho+para ), 7.16 (t, 3 J HH = 7.4 Hz, 1H, oTol meta ), 7.08 (t, 3 J HH= 7.4 Hz, 1H, oTol meta’ ), 3.82 (brs, 8H, Purple), 3.38 (brs, 12H Purple), 2.63 - 2.29 (m, 9H, CH3, oTol+PCy2, H3+Mor), 1.94 - 0.98 (m, 20H, PCy2)ppm. 13 C{ 1 H} NMR (101 MHz, CD2Cl2): δ = 143.1 (dd, 2 J CP = 7.1, 2.6 Hz, oTol ipso ), 139.3 (dd, 3 J CP = 4.7, 2.0 Hz, oTol ortho ), 138.1 (dd, 3 J CP = 7.7, 2.9 Hz, oTol ortho’ ), 131.45 (t, J CP = 1.7 Hz, oTol para ), 127.4 (t, J CP =2.5 Hz, oTol meta ), 125.8 (q, J CP = 2.5 Hz, oTol meta’ ), 67.2 (s, Mor, C2), 48.1 (s, Mor, C3), 41.5 (dd, 1 J CP = 37.6 Hz, 3 J CP = 2.1 Hz, PCy2, C1), 40.9 (dd, 1 J CP = 37.6 Hz, 3 J CP = 5.7 Hz, PCy2, C1), 35.3 (d, 3 J CP =3.3 Hz, PCy2, C3), 34.4 (d, 3 J CP = 2.7 Hz, PCy2, C3), 30.9 (s, PCy2, C3), 30.1 (d, 3 J CP= 1.7 Hz, PCy2, C3), 28.4 (d, 2 J CP = 14.0 Hz, PCy2, C2), 28.0 (d, 2 J CP = 14.1 Hz, 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 (162 MHz, CD2Cl2): δ = 50.2 (d, 2 J PP = 76.2 Hz, P(Mor)3), 34.0 (d, 2 J PP = 76.2 Hz, 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°C (decomposition). 32 H 53 Elemental analysis for AuClN3O3P2: Calculated: C 46.75, H 6.50, N 5.11; Found: C 46.45, H 6.38, N 4.98.

[0477] L17-AuCl:

[0478] [ka]

[0479] 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%).

[0480] 1 H NMR (400 MHz, CD2Cl2): δ = 7.38 - 7.31 (m, 12H, Ph ortho+meta ), 7.22 - 7.16 (m, 3H, Ph para ), 2.82 (d, 3 J HP = 8.2 Hz, 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 (101 MHz, CD2Cl2): δ = 146.9 (d, 2 J CP = 3.6 Hz, Ph ipso ), 129.5 (s, Ph meta ), 127.8 (d, 3 J CP =2.9 Hz, Ph ortho ), 126.0 (s, Ph para ), 42.3 (d, 2 J CP = 3.9 Hz, CH3NPh), 37.6 (dd, 1 J CP = 39.1 Hz, 3 J CP =4.6Hz, PCy2, C1), 31.8 (d, 3 J CP = 2.7 Hz, PCy2, C3), 31.4 (s, PCy2, C3), 27.9 (d, 2 J CP = 12.5 Hz, PCy2, C2), 27.5 (d, 2 J CP = 13.6 Hz, PCy2, C2), 26.6 (d, 4 J CP = 1.6 Hz,), 16.5 (d, 2 J CP = 8.0 Hz, PCPCH3), 13.8 (dd, 1 JCP = 213.4, 68.8 Hz, PCP)ppm. 31 P{ 1 H} NMR (162 MHz, CD2Cl2): δ = 51.9 (d, 2 J PP = 82.2 Hz, P(PhNMe)3), 38.2 (d, 2 J PP = 82.2 Hz, 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°C (decomposition). 35 H 49 Elemental analysis for AuClN3P2: Calculated: C 52.15, H 6.13, N 5.21; Found: C 52.12, H 6.16, N 5.14.

[0481] L1-Rh(acac)CO:

[0482] [ka]

[0483] 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 for 1 h. Single crystals of L1-Rh(acac)CO2 were obtained by slowly diffusing pentane into the concentrated solution in DCM.

[0484] 31 P NMR (162 MHz, C6D6): δ = 52.5 (d, 2 J PP = 78.9 Hz, P + Pip3), 39.5 (dd, 1 J RhP = 163.6 Hz,2 J PP = 78.5.1 Hz, PCy2).

[0485] L2-Rh(acac)CO:

[0486] [ka]

[0487] 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 for 1 h. Single crystals of L2-Rh(acac)CO2 were obtained by slowly diffusing pentane into the concentrated solution in DCM.

[0488] 31 P NMR (162 MHz, C6D6): δ = 62.4 (d, 2 J PP = 84.1 Hz, P + Pip3), 39.4 (br, PCy2).

[0489] L3-Rh(acac)CO:

[0490] [ka]

[0491] 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 for 1 h. Single crystals of L3-Rh(acac)CO2 were obtained by slowly diffusing pentane into the concentrated solution in DCM.

[0492] 31 P NMR (162 MHz, C6D6): δ = 77.8 (dd, 2 J PP = 66.2 Hz, 3 J RhP = 4.7 Hz, P+ Pip3), 39.4 (dd, 2 J PP = 66.2 Hz, 1 J RhP = 147.2 Hz, PCy2).

[0493] L1-Rh(CO)2 cyclometallation:

[0494] [ka]

[0495] 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 for 1 h. Single crystals of L1-Rh(CO)2 were obtained by slowly diffusing pentane into the concentrated solution in DCM.

[0496] 31 P NMR (162 MHz, CD2Cl2): δ = 79.6 (dd, 2 J PRh = 140.5 Hz, 2 J PP = 6.6 Hz, PCy2), 50.9 (dd, 2 J PP = 6.7 Hz, 3 J RhP = 10.6 Hz, P + Pip3). 1 H NMR (400 MHz, CD2Cl2) δ 7.54 (d, J = 7.18 Hzz), 6.71 (t, J = 7.49 Hz, 1H), 6.63 (d, J = 7.97 Hz, 1H), 6.24 (td, J = 7.11, 1.39 Hz, 1H), 3.59 - 2.67 (m, 14H), 2.15 - 1.18 (m, 48H). 13C NMR (101 MHz, CD2Cl2) δ 195.81 - 192.02 (m), 165.52 - 164.97 (m), 145.29 (d, J = 3.82 Hz), 124.56, 120.02 (d, J = 21.75 Hz), 115.92, 48.04, 38.91 (d, J = 26.31 Hz), 32.70 (d, J = 2.93 Hz), 30.40 (d, J = 4.40 Hz), 27.21 (dd, J = 42.63, 12.51 Hz), 26.24 (d, J = 4.12 Hz), 24.67.

[0497] L1-Ir(COD) cyclometallation:

[0498] [ka]

[0499] 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 for 1 h. Single crystals of L1-Ir(COD) were obtained by slow diffusion of pentane into the concentrated solution in THF.

[0500] 31 P NMR (162 MHz, THF): δ = 55.2 (d, 2 J PP = 6.4 Hz, PCy2), 54.6 (dd, 2 J PP = 6.3 Hz, P + Pip3).

[0501] L2-Ni(benzaldehyde):

[0502] [ka]

[0503] 200 mg (0.394 mmol) of L2 and 108 mg of Ni(COD)2 (0.394 mmol) were suspended in 4 ml of hexane, 0.08 ml of benzaldehyde (0.788, 2 equivalents) was added, and the reaction mixture was stirred for 30 min. An orange solid precipitated, which was filtered, washed with 3 × 4 ml of hexane, and dried in vacuo. 83.6 mg (0.194 mmol, 49.1%) of the complex was obtained as an orange solid. Single crystals of L2-Ni(benzaldehyde) were obtained by slowly diffusing pentane into a concentrated solution in THF.

[0504] 31 P NMR (162 MHz, THF): δ = 72.2 (d, 2 J PP = 116.2 Hz, PCy2), 26.8 (dd, 2 J PP = 116.2 Hz, P + Pip3). Comparison with the catalyst shown in WO 2019 / 030304

[0505] Monoarylation of acetone

[0506] [ka]

[0507] [Table 7]

[0508] Monoarylation of ammonia

[0509] [ka]

[0510] [Table 8]

Claims

1. A ligand of formula 1, 【Chemistry 1】 wherein R1 is each substituted or unsubstituted alkyl, perfluoroalkyl, aryl or cycloalkyl, cyano, or sulfonyl: —SO ２ -R10 (R10 = C1-C5 alkyl, C5-C6 cycloalkyl, or C5-C10 aryl), each of which is unsubstituted or substituted with C1-C4 alkyl or C1-C4 perfluoroalkyl; or silyl-: Si(RRR40), where R20, R30, and R40 are, independently of one another, C1-C6 alkyl, or C5-C10 aryl, each of which is unsubstituted or substituted with C1-C4 alkyl, R2 is alkyl, cycloalkyl, adamantyl, or aryl, each of which is substituted or unsubstituted; R3, R4, and R5 are alkyl, cycloalkyl, or aryl, each of which is unsubstituted or substituted; or at least two of R3, R4, and R5 are alkyl bridges or alkyl ether bridges that, together with the phosphorus atom, form a heterocyclyl ring; or R3 and R6, and / or R4 and R7, and / or R5 and R8 together form an alkyl bridge or an alkyl ether bridge, which together with the nitrogen atom to which they are attached form a heterocyclyl ring; R6, R7, and R8 are alkyl or aryl, which are unsubstituted or substituted, or which individually or collectively form a heterocyclyl ring with R3, R4, or R5 and the nitrogen atom to which they are attached; A ligand wherein m, n, and o are 0 or 1, provided that at least one of m, n, and o is 1.

2. R1 is C1-C9 alkyl, C4-C8 cycloalkyl, C5-C10 aryl, cyano, or sulfonyl: —SO ２ 2. The ligand of claim 1, wherein R1 is selected from: -R10 (R10 = C1-C5 alkyl, C5-C6 cycloalkyl, or C5-C10 aryl), each of which is unsubstituted or substituted with one or more C1-C4 alkyl, C1-C4 alkoxy, or C1-C4 perfluoroalkyl; or silyl: -Si(RR30R40), where R20, R30, and R40 are each 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 is optionally substituted with one or more C1-C5 alkyl, C1-C5 alkoxy, or C1-C5 perfluoroalkyl.

3. 2. The ligand of claim 1, wherein R2 is C1-C9 alkyl, C4-C8 cycloalkyl, adamantyl, C5-C10 aryl, which is unsubstituted or substituted with one or more C1-C5 alkyl, C1-C5 alkoxy, or C1-C5 perfluoroalkyl.

4. 2. The ligand of claim 1, wherein R3, R4, and R5 are, independently of one another, C1-C9 alkyl, C4-C8 cycloalkyl, adamantyl, C5-C10 aryl, which are unsubstituted or substituted with C1-C5 alkyl, C1-C5 alkoxy, or C1-C5 perfluoroalkyl, or at least two of R3, R4, and R5 are C2-C10 alkyl bridges, C2-C10 alkenyl bridges, or C2-C10 alkyl ether bridges, which, together with the phosphorus atom, form a heterocyclyl ring.

5. 2. The ligand of claim 1, wherein R3, R4, and R5 are, independently of one another, C1-C5 alkyl, C4-C8 cycloalkyl, adamantyl, C5-C6 aryl, which are unsubstituted or substituted with C1-C5 alkyl, C1-C5 alkoxy, or C1-C5 perfluoroalkyl, or at least two of R3, R4, and R5 are C2-C5 alkyl bridges, C2-C5 alkenyl bridges, or C2-C4 alkyl ether bridges, which, together with the phosphorus atom, form a heterocyclyl ring.

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

7. 2. The ligand of claim 1, wherein R6, R7, and R8 are C1-C9 alkyl or C5-C10 aryl, which are unsubstituted or substituted with one or more C1-C5 alkyl, C1-C5 alkoxy, or C1-C5 perfluoroalkyl, or which individually or collectively form a heterocyclyl ring together with R3, R4, or R5 and the nitrogen atom to which they are attached.

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

9. 2. The ligand of claim 1, wherein R1 represents C1-C9 alkyl, C4-C8 cycloalkyl, C5-C10 aryl, which aryl is unsubstituted or substituted with C1-C5 alkyl, C1-C5 alkoxy, or C1-C5 perfluoroalkyl.

10. 2. The ligand of claim 1, wherein R1 is selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert.butyl, n-pentyl, n-pentyl(amyl), 2-pentyl(sec-pentyl), 3-pentyl, 2-methylbutyl, 3-methylbutyl(iso-pentyl or iso-amyl), 3-methylbut-2-yl, 2-methylbut-2-yl, 2,2-dimethylpropyl(neopentyl), n-hexyl, trifluoromethyl, cyclobutyl, cyclopentyl, cyclohexyl, menthyl, phenyl, o-toluyl, naphthyl, o-methoxyphenyl, o-ethoxyphenyl, di-(o-methoxy)phenyl, p-trifluoromethylphenyl, trimethylsilyl, triisopropyl-silyl, tri-tert-butylsilyl, cyano, methylsulfonyl, toluenesulfonyl, and trifluoromethylsulfonyl.

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

12. 2. The ligand of claim 1, wherein R3, R4, R5, R6, R7, and R8 are each independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentylbutyl, n-pentyl, n-pentyl(amyl), 2-pentyl(sec-pentyl), 3-pentyl, 2-methylbutyl, 3-methylbutyl(iso-pentyl or iso-amyl), 3-methylbut-2-yl, 2-methylbut-2-yl, 2,2-dimethylpropyl(neopentyl), n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, mesityl.

13. 2. The ligand of claim 1, wherein at least two of m, n, and o are 1.

14. 2. The ligand of claim 1, wherein m, n, and o are all 1.

15. 2. The ligand of claim 1, R1 is C1-C9 alkyl or C5-C10 aryl, each of which is unsubstituted or substituted with C1-C4 alkyl, or sulfonyl: —SO ２ -R10 (R10 = C5-C10 aryl, which is unsubstituted or substituted with C1-C4 alkyl); R2 is C1-C9 alkyl, C4-C8 cycloalkyl, or adamantyl; R3, R4, and R5 are, independently of one another, C1-C9 alkyl, C4-C8 cycloalkyl, adamantyl, or C5-C10 aryl; R6, R7, and R8 are C1-C9 alkyl or C5-C10 aryl, which are unsubstituted or substituted with one or more C1-C5 alkyls; and / or Ligands in which R3 and R6, and / or R4 and R7, and / or R5 and R8, taken together, are a C2-C8 alkyl bridge, or a C2-C8 alkyl ether bridge, optionally wherein said C2-C8 alkyl bridge is part or all of a fused C4-C8 cycloalkyl ring.

16. 2. The ligand of claim 1, R1 is C1-C9 alkyl or C5-C10 aryl, each of which is unsubstituted or substituted with C1-C4 alkyl, or sulfonyl: —SO ２ -R10 (R10 = C5-C10 aryl, which is unsubstituted or substituted with C1-C4 alkyl); R2 is C1-C9 alkyl, C4-C8 cycloalkyl, or adamantyl; at least two of m, n, and o are 1; at least two of R3, R4, and R5 together are a C2-C8 alkyl bridge, or a C2-C8 alkyl ether bridge, optionally substituted with one or more C1-C5 alkyl or cycloalkyl groups, or the C2-C8 alkyl or C2-C8 alkyl ether bridge is part of a fused C4-C8 cycloalkyl ring, optionally forming a heterocyclyl ring together with the phosphorus atom; R6, R7, and / or R8 are C1-C6 alkyl or C5-C10 aryl that is unsubstituted or substituted with one or more C1-C5 alkyl; With the proviso that when 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.

17. 2. The ligand of claim 1, R1 is C1-C9 alkyl or C5-C10 aryl (each of which is unsubstituted or substituted with C1-C4 alkyl), or sulfonyl: —SO ２ -R10 (R10 = C5-C10 aryl, which is unsubstituted or substituted with C1-C4 alkyl); R2 is C1-C9 alkyl, C4-C8 cycloalkyl, or adamantyl; R3, R4, and R5 are, independently of one another, C1-C9 alkyl, C4-C8 cycloalkyl, adamantyl, or C5-C10 aryl; R6, R7, and R8 are C1-C9 alkyl or C5-C10 aryl, which are unsubstituted or substituted with one or more C1-C5 alkyls; and / or A ligand wherein R3 and R6, and / or R4 and R7, and / or R5 and R8, taken together, are a C2-C8 alkyl bridge, or a C2-C8 alkyl ether bridge, optionally wherein said C2-C8 alkyl bridge is part or all of a fused C4-C8 cycloalkyl ring.

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

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

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

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, mesityl.

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

25. 2. 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 ring or a morpholinyl ring.

26. 2. The ligand of claim 1, wherein R3 and R6, 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 any one of claims 1 to 26, optionally comprising at least one organic ligand L, and / or at least one halogen X.

28. Steps below: - 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; - reacting said substrate with said coupling partner in the presence of said metal complex or a derivative thereof to form a coupling product; A method for carrying out a coupling reaction, comprising:

29. 29. A method of carrying out a coupling reaction according to claim 28, wherein the metal complex comprising a ligand is a metal complex according to claim 27.

30. 30. The method of claim 28 or 29, wherein the coupling reaction can be selected from the group consisting of: (i) catalytic hydrofunctionalization reactions of alkynes and alkenes; (ii) catalytic hydroamination reactions of alkynes and alkenes; (iii) catalytic O—H addition reactions to alkynes and alkenes; (iv) catalytic coupling reactions; (v) catalytic Kumada, Murahashi, Negishi, or Suzuki coupling reactions, in particular reactions for the formation of biarylenes; (vi) catalytic cross-coupling reactions, in particular C—N and C—O coupling reactions; (vii) catalytic Heck coupling reactions, in particular for the preparation of arylated olefins, and Sonogashira coupling reactions, in particular for the preparation of arylated and alkenylated alkynes; and / or (viii) Catalytic α-arylation of carbonyl compounds and imines.

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