YLIDE-FUNCTIONALIZED PHOSPHANES FOR USE IN METAL COMPLEXES AND HOMOGENEOUS CATALYSIS

Description

[0001] The invention relates to ylide-functionalized phosphine ligands, their preparation and use in transition metal compounds and their use as catalysts in organic reactions. Hintergrund der Erfindung

[0002] The synthesis of complex molecules is often a central component in fine chemistry, for example, to obtain products for the production of pharmaceuticals, dyes, agrochemicals, materials, etc. This often requires catalytic processes for functionalization reactions, such as coupling reactions (Suzuki, Heck, Sonogashira, etc.) or hydrofunctionalization reactions (hydroamination, hydrosilylation, etc.) for the derivatization of olefins, aryls, or alkynes. The catalysis is decisively influenced by the metal and the ligands used.

[0003] Phosphanes are among the most widely used ligands in catalysis. Tuning their electronic and steric parameters is crucial for increasing catalyst activity, determining selectivity, and expanding substrate diversity (AC Hillier et al., Organometallics, 22: 4322 (2003); H. Clavier et al. Chem. Commun., 46: 841 (2010); ZL Niemeyer, A. Milo, DP Hickey, MS Sigman, Nature Chem. 8: 610 (2016); CA Tolman, Chem. Rev. 77, 313 (1977); G. Frenking, Organometallics, 28, 3901 (2009)). The variability of phosphanes and the manipulation of their electronic and steric properties favor them over many other ligand systems. Phosphanes are therefore used in a variety of reactions, such as palladium-catalyzed coupling reactions (MA Wünsche et al., Angew. Chem. Int. Ed., 54, 11857 ​​(2015); DS Surry et al., Angew. Chem. Int. Ed., 47, 6338 (2008); R. Martin et al., Acc. Chem. Res., 41, 1461 (2008); S. Kotha et al., Tetrahedron, 58, 9633 (2002)) or gold-catalyzed hydroamination reactions (Lavallo, V. et al.; Angew. Chem., Int. Ed., 52, 3172 (2013); E. Mizushima et al., Org. Lett., 5, 3349 (2003); Y. Wang et al., Nature. Commun., 1 (2014)). New active catalyst systems are based, among others, on adamantyl-functionalized phosphines (DE 10037961 A1, WO 02 / 10178 A1, L. Chen et al., J. Am. Chem. Soc., 138, 6392 (2016); CA Fleckenstein et al., Chem. Soc. Rev., 39, 694 (2010); KA Agnew-Francis et al., Adv. Synth. Catal., 358, 675 (2016)) or biaryl phosphine ligands (US 6307087 B1, DS Surry et al., Angew. Chem., 120, 6438 (2008); Angew. Chem. Int. Ed., 47, 6338 (2008); RA Altman et al., Nat. Protoc., 2, 3115 (2007); DS Surry et al., Chem. Sci., 2, 27 (2011); EJ Cho et al., Science, 328, 1679 (2010); DA Watson et al., Science, 325, 1661 (2009)). A review of important homogeneous catalysis with phosphine ligands can be found, for example, in B.Cornils, WA Hermann, Applied Homogenous Catalysis with Organometallic Compounds, Vol 12, VCH, Weinheim, 1996.

[0004] Ligand design is crucial in catalysis for enabling reactions or directing them in the desired direction. For example, the development of new phosphine ligands is often required to achieve more cost-effective starting substrates (e.g., chlorides instead of iodides), higher catalyst productivity and activities, and a broader substrate and reaction diversity.

[0005] Benn et al., Tetrahedron 1984 Vol. 40, No. 17, pp. 3273-3276 and Sergio Pascual et al., Angewandte Chemie International Edition 2007 Vol. 46, No. 47, pp. 9078-9080 show phosphinylide compounds, but no complexes formed with them.

[0006] Schmidbaur, Pure & Applied Chemistry 1980 Vol. 52, No. 4, pp. 1057-1062 shows a compound of the type (Phenyl) 2 P-CH=P(Phenyl) 2 -CH 2 -P(Phenyl) 2 as well as its sodium complex and alkaline earth metal complexes, but no corresponding transition metal complexes.

[0007] Jens Langer, Arkivoc Vol. 2012, No. 3, from 2011, p. 210 shows ylides in Table 3 as well as compound 2 and its lithium metal complex (compound 4).

[0008] Schmidbaur et al., Chemical Reports 1968, 101(10), 3545-3555, Pure and Applied Chemistry 1980, 52(4), 1057-1062, Angewandte Chemie 1979, 91(10), 848-850 and Chemical Reports 1984, 117(12), 3374-3380, Boldeskul et al., Teoreticcheskaya i Eksperimental'nya Khimiya 1979, 15(6), 727-731, Aggarwal et al., Science of Synthesis, 2005, 22, 11-73, Kolodyazhnyi, Zhurnal Obshchei Khimii 1975, 45(3), 704-705 and Lysenko et al., Zhurnal Obshchei Khimii 1979, 49(6), 1230-1235 show phosphorus-containing ylides, but no metal complexes of phosphinylides.

[0009] Organ et al., Synthesis Vol. 2008, No. 17, pp. 2776-2797 demonstrates the use of NHC-based ylides (which are not phosphorus ylides) for the preparation of noble metal / transition metal complexes and methods for carrying out coupling reactions with these complexes.

[0010] Scherpf et al., Angewandte Chemie International Edition 2018, Vol. 57, No. 39, pp. 12859-12864, demonstrates metal complexes of various ylides and their use as coupling catalysts. Gold was used exclusively as the metal.

[0011] Yogendra et al., Dalton Transactions, 2017, Vol. 46, No. 44, pp. 15503-15511, presents metal complexes of various ylides. Gold was used exclusively as the metal.

[0012] Schmidbaur et al., Angewandte Chemie 1988, Vol. 100, No. 3, pp. 439-441 and Helvetica Chimica Acta 1986, Vol. 69, No. 7, pp. 1748-1756, and Knoll, Zeitschrift für Naturforschung 1978, 33b, pp. 396-398, demonstrate various metal complexes with phosphane ligands. Exclusively gold or chromium were used as the metal. Detaillierte Beschreibung der Erfindung

[0013] It has now been found that the ylide-functionalized phosphine ligands of formulas (I) and (II) described below, with a carbanionic carbon center in the α-position to the phosphorus, and their transition metal complexes, fulfill the stated objective. The invention thus relates to:

[0014] Metal complexes of phosphine ligands having the formula (I) or (II) wherein On is a phosphonium group -P(R 3< R 4< R 5< ) wherein R 3< , R 4< and R 5< are independently selected from the group consisting of C 1-6 alkyl groups, C 4-C10 cycloalkyl groups, C 6-10 aryl groups, X 1< is selected from the group consisting of straight-chain, branched or cyclic C 1-6 alkyl groups, C 6-10 aryl groups, mono- or polyunsaturated, straight-chain, branched or cyclic C 2-6 alkenyl groups, a trialkylsilyl (-SiR 3< R 4< R 5< ), arylsulfonyl group (R 12< -SO 2 R 3< ) with R 12< = C 6-10 aryl) and R 1< and R 2< C 6-10 aryl groups or C 1-6 alkyl and cycloalkyl groups.

[0015] R 3<, R 4<, and R 5< can be independently selected from the group consisting of methyl, ethyl, butyl, cyclohexyl, phenyl, and combinations thereof. R 3<, R 4<, and R 5< can be identical and selected from the group consisting of methyl, ethyl, butyl, cyclohexyl, phenyl, and combinations thereof, especially cyclohexyl and phenyl.

[0016] X 1< can be selected from the group consisting of methyl, ethyl, cyclohexyl, phenyl, p-tolyl, trimethylsilyl, p-tolylsulfonyl or combinations thereof.

[0017] R 1< and R 2< can be independently selected from the group consisting of phenyl, cyclohexyl, methyl and combinations thereof.

[0018] These metal complexes are precious metal or transition metal complexes of group 10 or 11 of the periodic table of elements, namely copper, silver, platinum, palladium and nickel, especially palladium.

[0019] The noble metal or transition metal complexes and salts with the phosphine ligands described above can be used in homogeneous catalysis.

[0020] In particular, they can be used as catalysts, whereby the ligands in situ added to the metal, noble metal or transition metal precursor compounds or the isolated metal, noble metal or transition metal complexes of the phosphine ligands are used in the synthesis of transition metal complexes or transition metal salts.

[0021] In the above uses, the ligands (i) in catalytic hydrofunctionalization reactions of alkynes and alkenes; (ii) in catalytic hydroamination reactions of alkynes and alkenes; (iii) in catalytic OH addition reactions to alkynes and alkenes; (iv) in catalytic coupling reactions; (v) in catalytic Suzuki coupling reactions, in particular for the preparation of biaryls; (vi) in catalytic cross-coupling reactions, in particular CN and CO coupling reactions; and / or (vii) in 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; be used.

[0022] Likewise, R 1< and R 2< can be independently selected from the group consisting of phenyl, cyclohexyl, methyl, tert-butyl and combinations thereof.

[0023] Advantageous ligands can in particular be ligands of the above formulas (I) or (II) with the substituents according to the following Table A: Nr. R1, R2 On X 1 Tert.-Butyl PPh3 Phenyl 2 Phenyl PPh3 Phenyl 3 Methyl PPh3 Phenyl 4 Cyclohexyl PPh3 Phenyl 5 Tert.-Butyl PCy3 Phenyl 6 Phenyl PCy3 Phenyl 7 Methyl PCy3 Phenyl 8 Cyclohexyl PCy3 Phenyl 9 Tert.-Butyl PPh3 Methyl 10 Phenyl PPh3 Methyl 11 Methyl PPh3 Methyl 12 Cyclohexyl PPh3 Methyl 13 Tert.-Butyl PCy3 Methyl 14 Phenyl PCy3 Methyl 15 Methyl PCy3 Methyl 16 Cyclohexyl PCy3 Methyl 17 Tert.-Butyl PPh3 Trimethylsilyl 18 Phenyl PPh3 Trimethylsilyl 19 Methyl PPh3 Trimethylsilyl 20 Cyclohexyl PPh3 Trimethylsilyl 21 Tert.-Butyl PCy3 Trimethylsilyl 22 Phenyl PCy3 Trimethylsilyl 23 Methyl PCy3 Trimethylsilyl 24 Cyclohexyl PCy3 Trimethylsilyl 25 Tert.-Butyl PPh3 Toluoysulfonyl SO2Tol 26 Phenyl PPh3 Toluoysulfonyl SO2Tol 27 Methyl PPh3 Toluoysulfonyl SO2Tol 28 Cyclohexyl PPh3 Toluoysulfonyl SO2Tol 29 Tert.-Butyl PCy3 Toluoysulfonyl SO2Tol 30 Phenyl PCy3 Toluoysulfonyl SO2Tol 31 Methyl PCy3 Toluoysulfonyl SO2Tol 32 Cyclohexyl PCy3 Toluoysulfonyl SO2Tol where PPh3 stands for triphenylphosphine and PCy3 stands for tricyclohexylphosphine.

[0024] The metal complexes are precious metal or transition metal complexes of the metals copper, silver, platinum, palladium and nickel, preferably palladium

[0025] The metal complexes may also contain other ligands, such as neutral electron donor ligands, for example, dibenzylideneacetone (DBA), carbon monoxide (CO), NHC ligands, phosphines such as triphenylphosphine or tricyclohexylphosphine, and amines such as triethylamine or tributylamine. Charged ligands such as halogens, especially chloride, bromide, and iodide, or pseudohalides such as mesylate, triflate, and acetate may also be present. Substituted or unsubstituted aryl and allyl ligands may also be present, as may mono- or diolefins, which may be linear or cyclic, such as cyclooctadiene.

[0026] Advantageously, the metal complexes can additionally contain ligands selected from the group consisting of dibenzylideneacetone (DBA), carbon monoxide CO, triphenylphosphine, tricyclohexylphosphine, triethylamine, tributylamine, pyridyl, chloride, bromide, iodide, mesylate, triflate, acetate, allyl, phenyl, p-toluyl, o-toluyl, mesityl, cyclooctadiene, and combinations thereof.

[0027] In particular, metal complexes from the following Tables B to F can be used. Tabelle B

[0028] Table B shows platinum complexes with at least one of the 32 phosphine ligands listed in Table A and one or more of the ligands selected from the group consisting of dibenzylideneacetone (DBA), carbon monoxide CO, triphenylphosphine, tricyclohexylphosphine, triethylamine, tributylamine, pyridyl, chloride, bromide, iodide, mesylate, triflate, acetate, allyl, phenyl, p-toluyl, o-toluyl, mesityl, cyclooctadiene, and combinations thereof. Tabelle C

[0029] Table C shows palladium complexes with at least one of the 32 phosphine ligands listed in Table A and one or more of the ligands selected from the group consisting of dibenzylideneacetone (DBA), carbon monoxide CO, triphenylphosphine, tricyclohexylphosphine, triethylamine, tributylamine, pyridyl, chloride, bromide, iodide, mesylate, triflate, acetate, allyl, phenyl, p-toluyl, o-toluyl, mesityl, cyclooctadiene, and combinations thereof. Tabelle D

[0030] Table D shows nickel complexes with at least one of the 32 phosphine ligands listed in Table A and one or more of the ligands selected from the group consisting of dibenzylideneacetone (DBA), carbon monoxide CO, triphenylphosphine, tricyclohexylphosphine, triethylamine, tributylamine, pyridyl, chloride, bromide, iodide, mesylate, triflate, acetate, allyl, phenyl, p-toluyl, o-toluyl, mesityl, cyclooctadiene, and combinations thereof. Tabelle E

[0031] Table E shows copper complexes with at least one of the 32 phosphine ligands listed in Table A and one or more of the ligands selected from the group consisting of dibenzylideneacetone (DBA), carbon monoxide CO, triphenylphosphine, tricyclohexylphosphine, triethylamine, tributylamine, pyridyl, chloride, bromide, iodide, mesylate, triflate, acetate, allyl, phenyl, p-toluyl, o-toluyl, mesityl, cyclooctadiene, and combinations thereof. Tabelle F

[0032] Table F shows silver complexes with at least one of the 32 phosphine ligands listed in Table A and one or more of the ligands selected from the group consisting of dibenzylideneacetone (DBA), carbon monoxide CO, triphenylphosphine, tricyclohexylphosphine, triethylamine, tributylamine, pyridyl, chloride, bromide, iodide, mesylate, triflate, acetate, allyl, phenyl, p-toluyl, o-toluyl, mesityl, cyclooctadiene, and combinations thereof.

[0033] The metal complexes can be obtained in a manner known per se, for example by reacting metal salts or complexes which advantageously already carry desired further ligands (such as nickel tetracarbonyl, allyl palladium(II) chloride dimer, palladium acetate, palladium chloride or tris(dibenzylideneacetone)-dipalladium(0) x dibenzylideneacetone) with one or more phosphine ligands, optionally in a suitable solvent.

[0034] The metal complexes described above can be used in homogeneous catalysis, in particular in coupling reactions, where 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 OH addition reactions on alkynes and alkenes; (iv) catalytic coupling reactions; (v) catalytic Suzuki coupling reactions, in particular for the preparation of biaryls; (vi) catalytic cross-coupling reactions, in particular CN and CO coupling reactions; and / or (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

[0035] In addition, the metal complexes can be a palladium allyl complex of structure (V) or palladium aryl complex of structure (VI): with where X is an anion, R 1< , R 2< , X 1< may be as defined in the above points, R 33< , R 34< and R 35< may be independently selected from H, alkyl, aryl and heteroaryl groups, which may be unsubstituted or substituted with functional groups, or at least two of R 33< , R 34< and R 35< may form a carbocyclic ring having 5 to 14 carbon atoms,

[0036] Ar can represent a substituted or unsubstituted, in particular a substituted aryl group.

[0037] Here, R 33< , R 34< and R 35< , independently of one another, can be selected from straight-chain, branched or cyclic C 1-10 alkyl groups, preferably from C 1-6 alkyl groups or C 4-C10 cycloalkyl groups, the aryl groups can be selected from C 6-14 aryl groups, preferably from C 6-10 aryl groups, the alkenyl groups can be selected from mono- or polyunsaturated, straight-chain, branched or cyclic C 2-10 alkenyl groups, preferably from C 2-6 alkenyl groups, and the heteroaryl groups can be selected from C 6-14 heteroaryl groups, preferably from C 6-10 heteroaryl groups, which have 1 to 5 heteroatoms selected from N, O and S, where the aforementioned groups can all be substituted with functional groups and / or at least two of R 33< , R 34< and R 35< form a carbocyclic ring which is a C 4-C 10 cycloalkyl group or a C 6-14 aryl group, which may be substituted with one or more functional groups, and Ar may be selected from C 6-14 aryl groups, preferably from C 6-10 aryl groups, and the heteroaryl groups may be selected from C 6-14 heteroaryl groups, preferably from C 6-C 10 heteroaryl groups, which may have 1 to 5 heteroatoms selected from N, O and S, where the aforementioned groups may all be substituted with functional groups, and the functional groups may be selected from alkyl (-R 11< ), in particular C 1-6 alkyl groups, C 6-10 aryl (-R 12< ), halogen (-Hal), hydroxy (-OH), cyano (-CN), Alkoxy- (-OR 3< ), amino- (-NR 11< 2 , -NHR 11< , NH 2 ), mercapto- (-SH, -SR 11< ), where R 11< , independently of further radicals R 11< , is selected from C 1-6 alkyl radicals.

[0038] In particular, X can be selected from the group halogen, tosylate, nosylate and mesylate, specifically X can be selected from the group fluorine, chlorine, bromine, iodine, tosylate, nosylate and mesylate and / or aryl is selected from phenyl, m-tolyl, p-tolyl, o-tolyl, mesityl, 1,3-diisopropylphenyl.

[0039] Palladium complexes containing at least one of the phosphane ligands described above, in particular the described palladium allyl complexes and palladium aryl complexes can be used in homogeneous catalysis, in particular in coupling reactions, where 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 OH addition reactions on alkynes and alkenes; (iv) catalytic coupling reactions; (v) catalytic Suzuki coupling reactions, in particular for the preparation of biaryls; (vi) catalytic cross-coupling reactions, in particular CN and CO coupling reactions; and / or (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.

[0040] Furthermore, the patent application relates to a process for carrying out a coupling reaction comprising the steps Providing a reaction mixture comprising at least substrate, coupling partner, and at least one of the above metal complexes or a metal complex comprising one of the ligands described above; and reacting substrate with the coupling partner in the presence of the metal complex or its derivative to form a coupling product.

[0041] Here too, the metal of the metal complex, as described above, is a noble metal and / or a transition metal selected from the group consisting of copper, silver, platinum, palladium, nickel and combinations thereof.

[0042] The substrate can be a substituted aromatic compound; in particular, the substituted aromatic compound can be an aromatic or heteroaromatic compound. This can be substituted, among other things, with a leaving group or an unsaturated aliphatic group. It has proven useful if the leaving group is selected from the group consisting of halogen, tosylate, nosylate, and mesylate, and / or the unsaturated aliphatic group is selected from the group consisting of alkene or alkyne, in particular having 2 to 12, especially 2 to 8, carbon atoms.

[0043] The coupling partner may comprise an organometallic compound which may in particular be selected from the group consisting of organic boron compounds, organic lithium compounds, organic zinc compounds, organic lithium compounds and Grignard compounds, wherein advantageously the organometallic compound comprises at least one aromatic radical or wherein the organometallic compound comprises at least one unsaturated aliphatic radical, or wherein the organometallic compound comprises at least one saturated aliphatic radical.

[0044] The invention is further illustrated by the following examples. These represent examples of the preparation of ylide-functionalized phosphines, their transition metal complexes, and their use in catalysis and are in no way to be understood as limiting the scope of the invention. Beispiele Beispiel 1: Darstellung von Ylid-funktionalisierten Phosphanen A) Preparation via metalated ylides with monochlorophosphanes (Route A)

[0045] Preparation of the ylide-functionalized biscyclohexylphosphane with On = PPh 3 , R=R'=Cy, X = SO 2 Tol from the metalated ylide [Ph 3 PCSO 2 Tol]Na 2.05 g (4.5 mmol) of the metalated ylide [Ph 3 PCSO 2 Tol]Na were dissolved in 40 ml of THF and cooled to -50 °C. At this temperature 1.13 mL (5.4 mmol) of dicyclohexylchlorophosphane was slowly added to the yellow reaction solution, which eventually decolorized upon warming to room temperature. After removal of the solvent under vacuum, the resulting colorless solid was dissolved in 30 mL of toluene, and the suspension was filtered. Further reduction of the solvent led to the formation of a solid. This solid was filtered off, yielding the product as a colorless solid (yield: 1.97 g, 3.2 mmol, 71%).

[0046] 1< H-NMR (250 MHz, THF-d 8< ): δ = 0.78-1.29 (m, 10H, C H Cy ), 1.47-1.79 (m, 10H, C H cy), 2.13-2.23 (m, 2H, CH cy), 2.31 (s, 3H, C H STol ), 6.90-7.10 (m, 4H, C H STol , meta / ortho), 7.35-7.61 (m, 9H, C H PPh , meta / para), 7.65-7.78 (m, 6H, C H PPh , ortho). 31< P{ 1< H}-NMR (250 MHz, THF-d 8< ): δ = -5.79 (d, 2< J PP = 164.3 Hz: P Cy) , 25.58 (d, 2< J PP = 164.4 Hz; P Ph 3 ). TEP = 2055.1 cm -1< .

[0047] According to this procedure, the simple ylide-functionalized phosphanes were also prepared with: On = PPh 3 , X = SO 2 Tol, R=R'=Ph (T. Scherpf et al., Angew. Chem. Int. Ed., 54, 8542 (2015)), i Pr, adamantyl or cyclohexyl On = PPh 3 , X = CN, R=R'=Ph or Cy.

[0048] Furthermore, the bisylide-functionalized posphane Y 2 PPh with On = PPh 3 and X = CN was prepared according to this procedure. B) Preparation via the dichlorophosphane intermediate (Route A)

[0049] Preparation of the ylide-functionalized dimethylphosphane with On = PPh 3 , R=R'=Me, X = SO 2 Tol from the metalated ylide [Ph 3 PCSO 2 Tol]Na In a 50 mL Schlenk tube, 3.01 g (6.66 mmol) of the metalated ylide was dissolved in 35 mL of THF. Then, 0.70 mL (1.10 g, 7.99 mmol) of phosphorus trichloride was quickly added dropwise and heated to boiling for 5 min. After the reaction solution was stirred overnight, the solvent was removed under vacuum, and the solid was dissolved in dichloromethane. The suspension was then filtered through a filter cannula, and the solvent was again removed under vacuum. The precipitated solid was washed with benzene, filtered through a reverse frit, and dried under vacuum. The ylide-functionalized dichlorophosphane was thus obtained as a colorless solid (yield: 2.88 g, 5.44 mmol, 82%).

[0050] 1< H-NMR (500.1 MHz, CD 2 Cl 2 ): δ [ppm] = 2.37 (s, 3 H; CH 3 ), 7.04-7.07 (m, 2 H; CH Tol,meta ), 7.22-7.25 (m, 2 H; CH Tol,ortho ), 7.49-7.55 (m, 6 H; CH PPh,meta ), 7.64-7.69 (m, 3 H; CH PPh,para ), 7.71-7.77 (m, 6 H; CH PPh,ortho ). 13< C{ 1< H}-NMR (125.8 MHz, CD 2 Cl 2 ): δ [ppm] = 21.5 (s, CH 3 ), 62.9 (dd, 1< J CP = 111.8 Hz, 1< J CP = 91.8 Hz; C PCS ), 124.1 (dd, 1< J CP = 92.8 Hz, 3< J CP = 3.6 Hz; C PPh,ipso ), 129.1 (s, CH Tol,meta ), 129.2 (d, 3< J CP = 12.8 Hz; CH PPh,meta ), 129.7 (d, 4< J CP = 1.9 Hz; CH Tol,ortho ), 133.5 (d, 4< J CP = 2.9 Hz; CH PPh,para ), 135.2 (dd, 2< J CP = 10.2 Hz, 4< J CP = 1.9 Hz; CH PPh,ortho ), 142.4 (s, C Tol,para ), 143.9 (s, C Tol,ipso ). 31< P{ 1< H}-NMR (162.0 MHz, CD 2 Cl 2 ): δ [ppm] = 19.7 (d, 2< J PP = 110.1 Hz), 159.2 (br). In a 50 mL Schlenk tube, 299 mg (0.56 mmol) of the ylide-functionalized dichlorophosphane was dissolved in 10 mL of THF, and 2.35 mL (1.13 mmol, 0.48 M) of methyllithium in THF was slowly added. After stirring the solution overnight, the solvent was removed under vacuum, and the residue was dissolved in 15 mL of benzene. The suspension was then filtered with a filter cannula, and the solvent was again removed under vacuum. After drying under vacuum, the dimethylphosphane was isolated as a colorless solid (0.38 g, 0.78 mmol; 82%).

[0051] 1< H-NMR (500.1 MHz, C 6 D 6 ): δ [ppm] = 1.70 (s, 6 H; CH 3,PMe ), 1.96 (s, 3 H; CH 3,Tol ), 6.74-6.75 (m, 2 H; CH Tol,meta ), 6.96-6.99 (m, 6 H; CH PPh,meta ), 7.03-7.05 (m, 3 H; CH PPh,para ), 7.59-7.60 (m, 2 H; CH Tol,ortho ), 7.75-7.77 (m, 6 H; CH PPh,ortho ). 13< C{ 1< H}-NMR (125.8 MHz, C 6 D 6 ): δ [ppm] = 16.0 (dd, 1< J CP = 13.9 Hz, 3< J CP = 6.5 Hz; CH 3,PMe ), 21.1 (s, CH 3,Tol ), 42.2 (dd, 1<J CP = 107.8 Hz, 1< J CP = 53.7 Hz; C PCS ), 126.9 (s, CH Tol,ortho ), 128.3 (d, 3< J CP = 12.0 Hz; CH PPh,meta ), 128.6 (s, CH Tol,meta ), 131.7 (d, 4< J CP = 2.8 Hz; CH PPh,para ), 135.0 (dd, 2< J CP = 9.5 Hz, 4< J CP = 2.5 Hz; CH PPh,ortho ), 139.8 (s, C Tol,para ), 148.5 (s, C Tol,ipso ). 31< P{ 1< H}-NMR (162.0 MHz, C 6 D 6 ): δ [ppm] = -46.4 (d, 2< J PP = 146.5 Hz), 23.6 (d, 2< J PP = 146.5 Hz). TEP = 2059.7 cm -1< .

[0052] According to this procedure, the simple ylide-functionalized phosphanes with On = PPh 3 , X = SO 2 Tol or CN, R=R'= Ph, Me, iPr or Cy were prepared.

[0053] Furthermore, the bisylide-functionalized posphane Y 2 PCy with On = PPh 3 and X = CN was prepared according to this procedure. C) Preparation by phosphorylation and deprotonation of onium salts (Route B)

[0054] The corresponding onium salts are either commercially available or can be prepared by standard synthetic methods such as the quaternization of corresponding phosphane, sulfide, or amine precursors with alkyl halides and tosylates. The salts (such as A in the following scheme) can be deprotonated with metal bases such as potassium tert-butoxide, metal hydrides or lithium / sodium / potassium bis(trimethylsilyl)amide and reacted directly with the halogenophosphane to give the phosphanyl-substituted onium salt (e.g. B). This can be converted into the desired ylide-functionalized phosphine without further workup using an additional equivalent of base. Simple representatives can be obtained from the commercially available bis(diphenylphosphino)methane and bis(dicyclohexylphosphino)methane by quaternization with alkyl halides and subsequent deprotonation (J. Langer et al., ARKIVOC, 3, 210 (2012)). Other functionalizations can be realized according to the following scheme. Phosphines, sulfides, amines, imines, N -Heterocycles and sulfoxides proved to be suitable: D) Examples: Synthesis of methyl- (Z = Me), phenyl- (Z = Ph) and silyl-functionalized (Z = SiMe 3 ) ylide phosphanes

[0055] The onium salt A(here: ethyltriphenylphosphonium iodide) with X = Me and Hal = I can be prepared according to known literature procedures (MN Alberti et al., Org. Lett., 10, 2465 (2008)) or purchased (CAS: 4736-60-1). The formation of the ylide-functionalized phosphine Y Me PCy 2 with R=Cy proceeds according to: 1.90 g (4.50 mmol) of ethyltriphenylphosphonium iodide and 500 mg (12.5 mmol) of potassium hydride were added to 20 mL of THF. The suspension was heated to 60 °C for 4 hours, after which no further hydrogen evolution was observed. Subsequently, 1.60 g (5.0 mmol) of dicyclohexyl iodophosphane was added dropwise, and the mixture was heated to 60 °C for 16 hours. After removing the solvent in vacuo, 20 mL of hexane was added. The mixture was heated to boiling point and filtered while hot. The solvent was again removed in vacuo, and the remaining solid was dissolved in a minimal amount of a 1:1 mixture of hexane and toluene. By storing the solution at -75 °C for three days, the desired phosphane was isolated as an orange, crystalline solid (1.63 g, 3.35 mmol, 74%).

[0056] 1< H NMR: (400.1 MHz, CD 2 Cl 2 ): δ = 1.20-1.59 (m, 10H, Cy), 1.70-1.89 (m, 6H, Cy), 1.89-2.07 (m, 4H, Cy), 2.11 (dd, 3H, 3< J HP = 16.3 Hz, 3< J HP = 2.4 Hz, CH 3 ), 2.21-2.30 (m, 2H, Cy), 7.05-7.10 (m, 9H, C H PPh, ortho and C H PPh , para ), 7.69-7.79 (m, 6H, C H PPh , meta ), 31< P{ 1< H}-NMR: (162.1 MHz, , CD 2 Cl 2 ): δ = -2.44 (d, 2< J PP = 176.8 Hz, P Cy 2 ), 25.4 (d, 2< J PP = 176.8 Hz, P Ph 3 ). TEP: 2050.1 cm -1< .

[0057] The ylide-functionalized phosphanes with On = PPh 3 , X = Et, CH 2 Ph, Cy, SiMe 3 , R=R'= Ph, Me or Cy were also prepared according to this procedure. 2.00 g (4.20 mmol) of trimethylsilymethylenephenylphosphonium iodide and 250 mg (6.23 mmol) of potassium hydride were added to 20 mL of THF. The suspension was stirred at room temperature for 16 hours, after which no further hydrogen evolution was observed. The yellow suspension was filtered, washed with 5 mL of THF, transferred to a dropping funnel, and slowly added dropwise to a solution of dicyclohexyliodophosphane (1.5 g, 4.63 mmol) in 20 mL of toluene at -78 °C. The solution was slowly warmed to room temperature and then stirred for 24 h. The precipitated solid was filtered off, washed twice with 5 mL of toluene, and dried in vacuo. The solid and 670 mg of KHMDS (3.36 mmol) were dissolved in 20 mL of THF and stirred for 1 hour. The precipitated solid was removed by filtration, the solvent was removed in vacuo, and the remaining solid was dissolved in 50 ml of boiling hexane and filtered hot. The solution was slowly cooled to room temperature and allowed to stand for 16 hours.The solution above the resulting yellow crystals was removed, and the crystals were washed three times with 5 ml of cold hexane and then dried in vacuo. (1.07 g, 1.98 mmol, 47%).

[0058] 1< H NMR: (400.1 MHz, C 6 D 6 ): δ = 0.28 (s, 6.3 H, SiMe 3 , trans ) , 0.40 (s, 2.7 H, SiMe 3 , cis ), 0.89-2.25 (m, 20H, Cy, ) , 2.34-2.60 (m, 2H, Cy), 7.02-7.11 (m, 9H, C H PPh, ortho and C H PPh , para ), 7.73-7.82(m, 6H, C H PPh , meta ), 31< P{ 1< H}-NMR: (162.1 MHz, , C 6 D 6 ): δ = 8.3 (d, 2< J PP = 37.2 Hz, P Cy2, cis ) , 12.8 (d, 2< J PP = 172.2 Hz, P Cy2, trans ) , 19.7 (d, 2< J PP = 37.2 Hz, PPh 3 , cis ) , 29.1 (d, 2< J PP = 172.2 Hz, PPh 3 , trans ) ,. TEP: 2048.9 cm -1< . 4.00 g (10 mmol) of ethyltriphenylphosphonium iodide and 600 mg (15 mmol) of potassium hydride were added to 20 mL of THF. The suspension was stirred at room temperature for 16 hours, after which no further hydrogen evolution was observed. The red suspension was filtered, washed with 5 mL of THF, transferred to a dropping funnel, and slowly added dropwise to a solution of cyclohexyldichlorophosphane (460 mg, 2.5 mmol) in 20 mL of THF with vigorous stirring. The solution was stirred at room temperature for 16 h. The precipitated solid was filtered off and washed twice with 10 mL of THF. The solvent of the resulting red solution was removed in vacuo, and the resulting solid was dried in vacuo. 20 mL of cyclohexane was added, heated to boiling, filtered hot, and then slowly cooled to room temperature, whereupon a red solid precipitated. The supernatant solution was removed, and the solid was washed twice with 2 ml of pentane and dried in vacuo. (0.68 g, 0.98 mmol, 39%).

[0059] 1< H NMR: (400.1 MHz, C 6 D 6 ): δ = 1.17-1.36 (m, 3H, Cy, ) , 1.47-1.60 (m, 2H, Cy, ) , 1.70-1.80 (m, 1H, Cy, ) , 1.84-1.94 (m, 2H, Cy, ) , 2.22-2.32 (m, 2H, Cy), 2.52 (dd, 3< J HP = 17.4 Hz, 3< J HP = 2.0 Hz 6H, Me ), 2.75-2.86 (m, 1H, Cy), 7.98-7.04 (m, 12H, C H PPh , ortho ), 7.04-7.11 (m, 6H, C H PPh , para ), 7.62-7.70(m, 12H, C H PPh , meta ), 31< P{ 1< H}-NMR: (162.1 MHz, , C 6 D 6 ): δ = -20.3 (t, 2< J PP = 175.1 Hz, P Cy) , 19.5 (d, 2< J PP = 175.1 Hz, P Ph 3 ) In a Schlenk flask, 10.0 g (22.9 mmol) of ethyltricyclohexylphosphonium iodide were suspended in 75 ml of THF. The suspension was cooled to 0°C in an ice bath, and 14.5 ml (22.9 mmol) of a 1.58 M solution of n-BuLi in hexanes was added dropwise. The now clear solution was warmed to room temperature, and 2.45 mL (2.67 g, 11.5 mmol) of dicyclohexylphosphine chloride was added. A colorless solid precipitated immediately, and the suspension was heated to 60 °C for 16 h. The colorless solid was filtered off and washed twice with 20 mL of THF each time and stored under argon. The filtrate was dried in vacuo, and the resulting solid was dissolved in 100 mL of cyclohexane, filtered, and the cyclohexane was removed again in vacuo. After drying in vacuo, the product was isolated as a colorless solid (4.93 g, 9.77 mmol, 85%).

[0060] 1< H NMR (400 MHz, C 6 D 6 ) δ = 1.08 - 1.23 (m, 9H, C H 2, PCy3, H3 + H4 ), 1.32 - 1.43 (m, 2H, C H 2, PCy2, H4 ), 1.43 - 1.58 (m, 12H, C H 2, PCy3, H2 + PCy2, H2 + H3 ), 1.58 - 1.66 (m, 5H, C H 2, PCy3, H4 + PCy2 , H2 ), 1.67 - 1.79 (m, 6H, C H2, PCy3, H3 ), 1.76 - 1.83 (m, 2H, C H 2, PCy2, H4 ), 1.82 - 1.96 (m, 11H, C H 2, PCy3, H2 + PCy2, H2 + C H 3 ), 1.95 - 2.09 (m, 4H, C H 2, PCy3, H3 + C H , PCy2, H1 ), 2.11 - 2.23 (m, 2H, C H 2, PCy2, H2 ), 2.23 - 2.34 (m, 2H, C H 2, PCy2, H3 ), 2.34 - 2.52 (m, 3H, C H , PCy3, H1 ) ppm. 13< C { 1< H} NMR (101 MHz, C 6 D 6 ) δ = -1.7 (dd, 1< J CP = 108.8 Hz, 1< J CP = 21.1 Hz, P- C -< -P), 14.8 (dd, 2< J CP = 8.4 Hz, 2< J CP = 0.7 Hz, C H 3 ), 26.6 - 27.0 (m, C H 2 , PCy3, C4 ), 27.7 - 27.8 (m, C H 2, PCy2, C4 ), 27.8 (d, 3< J CP = 11.0 Hz, C H 2, PCy3, C3 ), 28.0 - 28.4 (m, C H 2, PCy3, C2 ), 28.5 (d, 3< J CP = 11.8 Hz, C H 2, PCy2, C3 ), 29.0 (d, 3< J CP = 8.1 Hz, C H 2, PCy2, C3 ), 32.9 (d, 2< J CP = 9.9 Hz,C H2, PCy2, C2 ), 33.67 (dd, 1< J CP = 49.5 Hz, 3< J CP = 8.9 Hz, CH, PCy3, C1 ) 33.69 (d, 2< J CP = 19.8 Hz, C H 2, PCy2, C2 ), 38.4 (dd, 1< J CP = 13.8 Hz, 3< J CP = 5.3 Hz, C H, PCy2, C1 ) ppm. 31< P { 1< H} NMR (162 MHz, C 6 D 6 ) δ = 1.0 (d, 2< J PP = 128.9 Hz, P Cy 2 ), 30.6 (d, 2< J PP = 128.9 Hz, P Cy 3 ) ppm. CHNS: Calculated: C: 76.14, H: 11.58. Measured: C: 75.62, H: 11.32. Recovery of ethyltricyclohexylphosphonium iodide

[0061] The colorless solid remaining after washing with THF was dried in vacuo and dissolved in 15 mL of DCM. The solution was filtered, and the solvent was removed in vacuo and dried. Ethyltricyclohexylphosphonium iodide was obtained as a colorless solid (4.27 g, 9.8 mmol, 85%). In a Schlenk flask, 2.55 g (5.84 mmol) of ethyltricyclohexylphosphonium iodide was suspended in 25 ml of THF. The suspension was cooled to 0°C in an ice bath, and 2.78 ml (5.84 mmol) of a 2.1 M solution of nBuLi in hexanes was slowly added dropwise. The now clear solution was warmed to room temperature. 0.55 ml (0.53 g, 2.92 mmol) of di- tert butylchlorophosphane was added and heated to 60 °C for 16 h. The colorless solid was filtered off and washed twice with 5 ml of THF each. The filtrate was dried under vacuum, and the resulting solid was dissolved in 50 ml of cyclohexane. After further filtration, the solvent was removed under vacuum, and the product was isolated as a colorless solid (1.32 g, 1.51 mmol, 52%; unoptimized yield).

[0062] 1< H NMR (400 MHz, C 6 D 6 ) δ = 1.08 - 1.24 (m, 9H, C H 2, Cy, H3 + H4 ), 1.54 (d, 3< J HP = 10.7 Hz, 18H, C H 3, tBu), 1.44 - 1.67 (m, 9H, C H 2, Cy, H2 + H4 ), 1.63 - 1.76 (m, 6H, C H 2, Cy, H3 ), 2.04 (d, 3< J PH = 13.0 Hz, 6H, C H 2, Cy, H2 ), 2.11 (dd, 3< J HP = 13.8 Hz, 3< J HP = 3.1 Hz, 3H, C H 3 ), 2.16 - 2.32 (m, 3H, C H , Cy, H1 ) ppm. 13< C { 1< H} NMR (101 MHz, C 6 D 6 ) δ = 4.5 (dd, 1< J CP = 102.9 Hz, 1< J CP = 27.3 Hz, P- C -< -P), 18.2 (dd, 2< J CP = 8.6 Hz, 2< J CP = 0.6 Hz, CH 3 ), 27.0 ( C H 2, Cy, C4 ), 28.2 (d, 3< J CP = 10.6 Hz, C H 2, Cy, C3 ), 29.6 - 29.8 (m, C H 2, Cy, C2 ), 33.3 (d, 2< J CP = 14.4 Hz, CH3, t Bu), 36.5 (dd, 1< J CP = 23.4 Hz, 1< J CP = 6.6 Hz, C , t Bu ) 37.0 (dd, 1< J CP = 47.9 Hz, 3< J CP = 9.0 Hz, CH, Cy, C1 ) ppm. 31< P { 1< H} NMR (162 MHz, C 6 D 6 ) δ = 26.4 (d, 2< J PP = 146.9 Hz, Pt Bu 2 ), 30.4 (d, 2< J PP = 146.9 Hz, P Cy 3 ) ppm.

[0063] In a Schlenk tube, 500 mg (1.11 mmol) of benzyltricyclohexylphosphonium iodide was weighed and suspended in 10 mL of THF. 0.51 mL (1.11 mmol; 1 eq.) of an n-BuLi solution (2.18 M in hexane) was slowly added dropwise to the suspension until a clear solution had formed. The solution was stirred for 45 min, and then 0.32 mL (335 mg; 1.44 mmol; 1.3 eq.) of Cy 2 PCl was added dropwise. The suspension was stirred for 16 h at room temperature. The solid was filtered off and washed twice with 10 mL of THF each time and dried for 1.5 h under high vacuum (558 mg). The resulting solid and 133 mg (1.19 mmol) of potassium tert-butoxide was weighed into a Schlenk tube and suspended in 20 mL of dry toluene. The suspension was stirred for 16 h and then filtered. The solid was washed twice with 10 mL of toluene. The solvent from the filtrate was removed under vacuum, and the product was obtained as a colorless solid (0.35 g, 0.62 mmol, 56%; non-optimized yield).

[0064] 1< H NMR (400 MHz, Tol-d 8 ) δ = 1.00 - 1.22 (m, 9H, C H 2, PCy3, H3 + H4 ), 1.22 - 1.64 (m, 19H, C H 2, PCy2, H2 + H3 + H4 PCy3, H2, H3 ), 1.64- 1.83 (m, 12H, C H 2, PCy2, H3 + H4 PCy3, , H3 ), 1.83- 2.01 (m, 10H, C H 2, PCy2, H2 PCy3, , H2 ), 2.33-2.46 (m, 5H, C H , PCy2, H1, PCy3, H1 ), 6.97- 7.00 (m, 1H, C H , Ph, para ), 7.18-7.25 (m, 2H, CH, Ph, meta), 7.34- 7.40 (m, 2H, C H , Ph, ortho) ppm. 31< P{ 1< H}-NMR (162.1MHz, Tol-d 8 ): δ [ppm]= -5.4 (d, 2< J PP = 132.0 Hz, PtBu 2 ), 21.5 (d, 2< J PP = 132.0 Hz,) ppm. Example 2: Preparation of transition metal complexes of ylide-functionalized phosphanes A) Nickel carbonyl complexes

[0065] As an example, the synthesis of the complex with the ylide-functionalized dimethylphosphane prepared from Example 1.B) with On = PPh 3 , R=R'=Me, X = SO 2 Tol is described here.

[0066] In a 30 mL Schlenk tube, 0.10 g (0.20 mmol) of the phosphine was suspended in 5 mL of pentane. Then, 0.43 mL (0.31 mmol) of 0.7 M nickel tetracarbonyl in benzene was quickly added dropwise, and the reaction mixture was stirred at room temperature for 2 h. The solvent was then removed via cannula, and the solid was washed twice with 5 mL of pentane each time. After removal of the solvent and drying in vacuo, the complex was obtained as a grayish solid (79.1 mg, 0.13 mmol, 61%).

[0067] 1< H-NMR (500.1 MHz, CD 2 Cl 2 ): δ [ppm] = 1.97 (d, 2< JPH = 4.70 Hz, 6 H; CH 3,PMe ), 2.30 (s, 3 H; CH 3,Tol ), 6.93-6.95 (m, 2 H; CH Tol,meta ), 7.16-7.17 (m, 2 H; CH Tol,ortho ), 7.38-7.42(m, 6 H; CH PPh,meta ), 7.53-7.58(m, 9 H; CH PPh,ortho+para ). 13< C{ 1< H}-NMR (125.8 MHz, CD 2 Cl 2 ): δ [ppm] = 21.4 (s, CH 3,Tol ), 23.4 (dd, 1< J CP = 26.8 Hz, 3< J CP = 3.5 Hz; CH 3,PMe ), 39.1 (dd, 1< J CP = 105.6 Hz, 1< J CP = 3.2 Hz; C PCS ), 125.9 (s, CH Tol,ortho ), 126.9 (dd, 1< J CP = 91.5 Hz, 3< J CP = 1.9 Hz; C PPh,ipso ), 128.8 (d, 3< J CP = 12.4 Hz; CH PPh,meta ), 129.0 (s, CH Tol,meta ), 132.8 (d, 4< J CP = 3.0 Hz; C PPh,para ), 135.1 (d, 2< J CP = 9.8 Hz; CH PPh,ortho ), 140.7 (s, C Tol,para ), 146.7 (dd, 3< J CP = 1.21 Hz, 3< J CP = 1.2 Hz; CH Tol,ipso ), 196.2 (s, Cco). 31< P{ 1< H}-NMR (162.0 MHz, CD 2 Cl 2 ): δ [ppm] = -11.8 (d, 2< J PP = 75.6 Hz), 20.3 (d, 2< JPP = 75.6 Hz) Elemental analysis: measured: C, 58.41; H, 4.51; S, 4.97. calculated: C, 58.80; H, 4.46; S, 5.06. B) Gold chloride complexes (not covered by the invention)

[0068] As an example, the synthesis of the complex with the ylide-functionalized diphenylphosphane prepared from Example 1.A. with On = PPh 3 , R=R'=Ph, X = SO 2 Tol is described here. In a 50 mL Schlenk tube, 0.20 g (3.26 mmol) of the phosphine and 0.11 g (3.26 mmol) of (THT)AuCl (THT = tetrahydrothiophene) were dissolved in 5 mL of THF. The reaction mixture was stirred overnight at room temperature, during which a colorless precipitate formed. The solid was filtered through an inverted frit and dried in vacuo to afford the desired gold complex (0.32 g, 0.38 mmol, 77%).

[0069] 1< H-NMR (500.1 MHz, CD 2 Cl 2 ): δ [ppm] = 2.27 (s, 3 H; CH 3 ), 6.20-6.23 (m, 2 H; CH Tol,ortho ), 6.70-6.72 (m, 2 H; CH Tol, 7.1, 7.1 m ). H; CH PPh,ortho+meta ), 7.61-7.62 (m, 2 H; CH AuPPh,para ), 7.63 - 7.66 (m, 7 H; CH AuPPh,meta+PPh,para ), 7.86-7.90 (m, 4H; CHAuPPh,ortho). 13< C{ 1< H}-NMR (125.8 MHz, CD 2 Cl 2 ): δ [ppm] = 21.3 (s, CH 3 ), 42.8 (dd, 1< J CP = 101.4 Hz, 1< J CP = 57.6 Hz; C PCS ), 126.0 (dd, 1< J CP = 86.9 Hz, 3< J CP = 8.8 Hz; CPPh,ipso), 126.0 (s, CH Tol,ortho ), 128.5 (dd, 2< J CP = 11.7 Hz, 4< J CP = 0.8 Hz; CH PPh,ortho ), 128.9 (s, CH Tol,meta ), 129.1 (d, 3< J CP = 12.5 Hz; C PPh,meta ), 131.1 (d, 4< J CP = 2.6 Hz; CH AuPPh,para ), 133.4 (d, 4< J CP = 2.8 Hz; CH PPh,para ), 133.4 (dd, 1< J CP = 63.0 Hz, 3< J CP = 8.2 Hz; C AuPPh,ipso ), 135.2 (d, 3< J CP = 13.6 Hz; CH AuPPh,meta ), 135.4 (dd, 2<J CP = 9.2 Hz, 4< J CP = 1.2 Hz; CH AuPPh,ortho ), 141.7 (s, C Tol,para ), 144.4 (s, CH Tol,ipso ). 31< P{ 1< H}-NMR (162.0 MHz, CD 2 Cl 2 ): δ [ppm] = 21.4 (d, 2< J PP = 68.3 Hz), 22.1 (d, 2< J PP = 68.3 Hz). Elemental analysis: measured: C, 54.19; H, 3.90; S, 3.68. Calculated: C, 53.88; H, 3.81; S, 3.78.

[0070] All gold-phosphine complexes used in catalysis (see below) were prepared according to this procedure. C) Palladium allyl complexes

[0071] The synthesis of three palladium allyl complexes of ylide-substituted phosphanes is described here as examples. Complexes with ligands other than those listed here can be prepared according to the procedures described. Synthesis of the complex with the ylide-functionalized diphenylphosphine prepared from Example 1.A) with On = PPh 3 , R=R'=Ph, X = SO 2 Tol:. In a 50 mL Schlenk tube, 201 mg (0.325 mmol) of the phosphine YS PPh 2 and 59 mg (0.163 mmol) of the allylpalladium(II) chloride dimer were dissolved in 10 mL dichloromethane and stirred for 1 h at room temperature. The solvent was then reduced to 1 mL under vacuum, and the mixture was treated with pentane until a solid precipitated. This was filtered through a reverse frit and then dried under vacuum, yielding the palladium complex as a brownish solid (163 mg, 0.21 mmol, 63%).

[0072] 1< H-NMR (500.1 MHz, CD 2 Cl 2 ): δ [ppm] = 1.8-2.5 (br, 2H; CH 2,allyl ), 2.22 (s, 3 H; CH 3 ), 2.76 (br, 1 H; CH 2,allyl ), 4.12 (m, 1 H; CH 2,allyl ), 4.84 (br, 1H; CH allyl ), 6.71- 6.73 (m, 2 H; CH Tol,meta ), 6.76-6.78 (m, 2 H; CH Tol,ortho ), 7.16-7.18 (m, 4 H; CH PdPPh,meta ), 7.22-7.25 (m, 2 H; CH PdPPh,para ), 7.41-7.45 (m, 6 H; CH PPh,meta ), 7.53-7.57 (m, 3H; CH PPh,para ), 7.84-7.88 (m, 4H; CH PdPPh,ortho ), 7.97-8.01 (m, 6H; CH PPh,ortho ). 13< C{ 1< H}-NMR (125.8 MHz, CD 2 Cl 2 ): δ [ppm] = 21.3 (s, CH 3 ), 42.3 (dd, 1< J CP = 105.2 Hz, 1< J CP = 20.4 Hz; C PCS ), 64.7 (br; CH 2,allyl ), 78.3 (d, 2< J CP = 31.8 Hz; CH 2,allyl ), 117.7 (d, 2< J CP = 4.3 Hz; CH allyl ), 126.5 (s, CH Tol,ortho ), 127.4 (d, 2< J CP = 10.3 Hz; CHPdPPh,meta), 128.3 (dd, 1< J CP = 94.0 Hz, 3< J CP = 1.2 Hz; C PPh,ipso ), 128.4 (dd, 1< J CP = 55.1 Hz, 3< JCP = 12.4 Hz; CH PdPPh,ipso ), 128.5 (s, CH Tol,meta ), 128.5 (d, 3< J CP = 12.8 Hz; CH PPh,meta ), 129.4 (d, 4< J CP = 2.0 Hz; CH PdPPh,para ), 132.3 (d, 4< J CP = 3.0 Hz; CH PPh,para ), 135.2 (d, 2< J CP = 10.5 Hz; CH PdPPh,ortho ), 136.2 (d, 2< J CP = 10.1 Hz; CH PPh,ortho ), 140.9 (s, C Tol,para ), 144.2 (s, C Tol,ipso ). 31< P{ 1< H}-NMR (162.0 MHz, CD 2 Cl 2 ): δ [ppm] = 9.9 (d, 2< J PP = 67.3 Hz), 22.9 (d, 2< J PP = 67.3 Hz). Synthesis of the complex with the ylide-functionalized dicyclohexylphosphine prepared from Example 1.D) with On = PCy 3, R=R'=Cy, X = Me: The phosphine Y* Me PCy 2 (300 mg, 0.60 mmol) and allylpalladium(II) chloride dimer (109 mg, 0.30 mmol) were dissolved in 7 mL of toluene and stirred until a clear solution formed. Stirring was discontinued, and the solution was stored at room temperature for 3 days. Yellow crystals slowly formed, which were separated from the solvent, then washed three times with 5 mL of pentane, and dried in vacuo (230 mg, 0.33 mmol, 56%; non-optimized yield).

[0073] 1< H NMR (400 MHz, CD 2 Cl 2 ) δ = 1.12 - 1.58 (m, 25H, C H 2, PCy3 + PCy2 ), 1.62 (dd, 3< J HP = 12.4 Hz, 3< J HP = 8.3 Hz, 3H, CH 3 ), 1.67 - 2.05 (m, 25H, C H 2, PCy3 + PCy2 ), 2.10 - 2.24 (m, 2H, C H , PCy2, H1 ), 2.43 - 3.70 (vbr, 2H, C H 2 , C3H5 ), 2.54 - 2.72 (m, 3H, CH , PCy3, H1 ), 3.54 (dd, 2< J HH = 13.7 Hz, 3< J HH = 8.5 Hz, 1H, C H 2, C3H5 ), 4.25 - 4.40 (m, 1H, C H 2, C3H5 ), 5.19 - 5.41 (m, 1H, CH, C3H5 ) ppm. 13< C { 1< H} NMR (101 MHz, CD 2 Cl 2 ) δ = -2.7 (dd, 1< J CP = 112.1, 1< J CP = 46.8 Hz, P- C -< -P), 16.4 (m, C H 3 ), 26.9 (d, 4< J CP = 1.5 Hz, C H 2 , PCy3, C4 ), 27.2 - 27.5 (m, C H 2, PCy2, C4 ), 27.8 (d, 3< J CP = 13.4 Hz, C H 2, PCy2, C3 ), 28.1 (d, 3< J CP = 11.3 Hz, C H 2, PCy3, C3 ), 28.60 (d, 3< J CP = 9.9 Hz, C H 2, PCy2, C3 ), 28.63 (d, 2< J CP = 2.6 Hz, C H 2, PCy3, C2 ), 30.0 - 30.5 (m, C H 2, PCy2, C2 ), 31.2 (d, 2< J CP = 5.2 Hz, C H 2, PCy2, C2 ), 32.7 - 36.6 (m, C H, PCy2, C1 ), 38.4 - 39.6 (br, C H, PCy3, C1 ), 52.5 - 52.9 (m,C H 2, C3H5 ), 79.5 (d, 2< J CP = 28.4 Hz, C H 2, C3H5 ), 114.9 (d, 2< J CP = 4.4 Hz, C H, C3H5 ) ppm. 31< P { 1< H} NMR (162 MHz, CD 2 Cl 2 ) δ = 20.5 (d, 2< J PP = 63.5 Hz, P Cy 2 ), 31.5 (d, 2< J PP = 63.5 Hz, P Cy 3 ) ppm. CHNS: Calculated: C: 61.13, H: 9.23. Measured: C: 61.03, H: 9.34. Synthesis of the complex with the ylide-functionalized phosphane prepared from Example 1.D) with On = PCy3, R=R'=tBu, X = Me: The phosphane Y* Me P t Bu 2 (300 mg, 0.66 mmol) and allylpalladium(II) chloride dimer (115 mg, 0.32 mmol) were dissolved in 10 mL of toluene and stirred at room temperature for 16 h. An orange solid formed, which was filtered off, washed with 10 mL of toluene, and then dried in vacuo (265 mg, 0.42 mmol, 66%).

[0074] 1< H NMR (400 MHz, CD 2 Cl 2 ) δ = 1.02 - 1.56 (m, 15H, C H2, Cy, H2 + H3 + H4 ), 1.21 (d, 3< J HP = 13.0 Hz, 9H, C H 3, t Bu ), 1.47 (d, 3< J HP = 13.3 Hz, 9H, C H 3, t Bu ), 1.57 - 1.67 (m, 3H, C H 2, Cy, H4 ), 1.68 - 1.89 (m, 9H, C H 2, Cy, H3 + C H 3 ), 1.84 - 1.99 (br, 3H, C H 2, Cy, H2 ), 2.08 - 2.20 (br, 3H, C H 2, Cy, H2 ), 2.69 - 2.99 (br, 3H, C H , Cy, H1 ), 2.91 - 3.85 (vbr, 2H, C H 2, C3H5 ), 3.56 (dd, 2< J HH = 13.5 Hz, 3< J HH = 8.4 Hz, 1H, C H 2 , C3H5 ), 4.27 - 4.35 (m, 1H, C H 2 , C3H5 ), 5.16 - 5.62 (m, 1H, C H, C3H5 ). 13< C { 1< H} NMR (101 MHz, CD 2 Cl 2 ) δ = 4.0 (dd, 1< J CP = 105.1 Hz, 1< J CP = 41.3 Hz, P- C -< -P), 18.0 - 19.5 (m, CH 3 ), 26.9 (d, 4< J CP = 1.5 Hz, C H 2 , PCy3, C4 ), 27.9 (d, 3< J CP = 12.4 Hz, C H 2, Cy, C3 ), 28.4 (d, 3<J CP = 11.0 Hz, C H 2, Cy, C3 ), 29.0 ( C H 2, Cy, C2 ), 29.6 ( C H 2, Cy, C2 ), 31.6 ( C H3, t Bu), 32.9 ( C H3, t Bu), 34.4 (d, 1< J CP = 48.1 Hz, C H, Cy, C1 ), 42.0 - 42.3 (m, C , t Bu ), 56.3 (d, 2< J CP = 2.4 Hz, C H 2, C3H5 ), 79.1 - 79.7 (m, C H2, C3H5 ), 113.7 ( C H, C3H5 ) ppm. 31< P { 1< H} NMR (162 MHz, CD 2 Cl 2 ) δ = 30.8 (d, 2< J PP = 63.4 Hz, P Cy 3 ), 58.0 (br, Pt Bu 2 ) ppm. CHNS: Calculated: C: 58.58, H: 9.36. Measured: C: 58.85, H: 9.31. D) Palladium(0) complexes and their oxidative addition products

[0075] As an example, the synthesis of the palladium dibenzylideneacetone complex with the ylide-functionalized dicyclohexylphosphine prepared from Example 1.D) with On = PCy 3, R=R'=Cy, and X = Me is described here. Analogous palladium complexes can be synthesized using corresponding procedures with all other phosphine ligands. A J. Young An NMR tube was filled with 30 mg (59 µmol) of the phosphine Y* MePCy 2 and 34 mg (59 µmol) of tris(dibenzylideneacetone)dipalladium(0) x dibenzylideneacetone. Both solids were suspended in 0.6 mL of deuterated THF and shaken for 30 minutes. The reaction was monitored by NMR spectroscopy, and after completion of the reaction, the product was crystallized by slowly diffusing pentane into the THF solution. The product was obtained as red crystals (45 mg; 53 µmol; 89%). Using an excess of phosphine ligand, the bisphosphine palladium(0) complex could also be isolated.

[0076] 31< P { 1< H} NMR (162 MHz, THF- d 8 ) δ = 26.9 (d, 2< J PP = 82.1 Hz, P Cy 2 ) , 31.6 (d, 2< J PP = 82.1 Hz, P Cy 3 ). 1< H NMR (400 MHz, THF-d8) δ = 1.02 - 1.86 (m, 50H), 1.53 (dd, 2< J HP = 12.6 Hz, 2< J HP = 7.2 Hz, 3H), 1.87 - 2.06 (m, 2H, C H , PCy2, H1 ), 2.09 - 2.32 (m, 3H, C H , PCy3, H1 ), 5.97 - 6.17 (m, 2H, dba), 6.35 - 6.73 (m, 2H, dba), 7.10 - 7.31 (m, 8H, dba), 7.30 - 7.43 (m, 8H, dba), 7.49 - 7.63 (m, 4H, dba), 7.63 - 7.73 (m, 8H, dba), 7.73 - 7.79 (m, 2H, dba).

[0077] As an example, the synthesis of a palladium(II) arylchlorido complex with the ylide-functionalized dicyclohexylphosphine prepared from Example 1.D) with On = PCy 3, R=R'=Cy, and X = Me is described here. Further palladium(II) complexes can be synthesized analogously with all other phosphine ligands as well as with other aryl chlorides and bromides. Phosphane Y* Me PCy 2 (500 mg, 0.99 mmol, 1 eq.) and bis(dibenzylideneacetone)palladium(0) (742 mg, 1.09 mmol) were stirred at RT in 10 mL of THF for 30 minutes. The solution was filtered, and 1 mL p -Chlorotoluene was added, and the solution was stirred for 48 h. The dark yellow precipitate was filtered off and washed three times with 10 ml of THF. After drying in vacuo, the product was obtained as a dark yellow solid (515 mg, 0.69 mmol, 70%). The complex was found to be insoluble in all common solvents except DCM, in which it slowly decomposed.

[0078] 31< P { 1< H} NMR (162 MHz, CD 2 Cl 2 ) δ = 32.5 (d, 2< J PP = 49.6 Hz), 35.1 (d, 2< J PP = 49.6 Hz) ppm. 1< H NMR (400 MHz, CD 2 Cl 2 ) δ = 0.95 - 2.08 (m, 52H, C H + C H 2, PCy2 + PCy3 ), 1.55 (dd, 3< J HP = 12.8 Hz, 3< J HP = 9.4 Hz, 3H, C H 3 ), 2.14 (s, 3H, C H 3 , Tolyl), 2.57 (br, 3H, C H , PCy3, H1 ), 6.68 (m, 2H, C H , Tolyl), 7.08 (m, 2H, C H , Tolyl ) ppm. Example 3: Transition metal-catalyzed reactions with ylide-functionalized phosphines A) Gold-catalyzed hydroamination of alkynes (not covered by the invention)

[0079] For this purpose, the phosphane gold chloride complexes prepared according to the procedure in Example 2.B) were dissolved in a 1:1 mixture of alkyne and amine, and one equivalent of sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate was added. The mixture was reacted under the conditions listed in the table below, resulting in the following conversions and yields. The catalysis showed no decrease in yield under aqueous conditions or upon exposure of the reaction mixture to air.

[0080] Table 1: Gold(I)-catalyzed hydroamination of phenylacetylene with aniline and ylide-functionalized phosphines. Approach Catalyst L AuCl; L = Amount of catalyst [mol%] Reaction time [h] Temperature [°C] Yield a< [%] 1 PPh 3 5 18 RT 20 b< 2 VS PPh 2 5 0.25 RT 70 3 VS PPh 2 1 0.25 RT 63 4 VS PPh 2 1 6 RT 99 5 YS PPh 2 0.1 2.5 50 66 6 VS PPh 2 0.1 5 50 82 isolated 6 VS PPh 2 0.1 14 50 94 7 VS PPh 2 0.05 22 50 59 8 VS PPh 2 0.01 22 50 28 6 _[a] - 24 50 - 7 VS PMe 2 0.1 24 50 90 8 YS PMe 2 0.05 24 50 76 9 YS PCy 2 1 0.25 RT 98 10 YS PCy 2 0.1 6 RT 61 11 YS PCY 2 0.1 22 RT 94 12 YS PCy 2 0.1 5 50 95 13 YS PCY 2 0.05 5 50 89 14 YS PCY 2 0.05 22 50 99 15 YS PCY 2 0.025 22 50 91 16 YS PCy 2 0.01 22 50 51 17 YS PCy 2 0.01 48 50 74 18 YS PCy 2 0.005 22 80 50 19 YS PCy 2 0.005 48 80 62 20 Y Si PCy 2 0.1 2 50 97 a) The yield was determined by NMR spectroscopy. b) D. Malhotra et al. Angew. Chem. Int. Ed. 53, 4456 (2014). B) Gold-catalyzed intramolecular OH addition to alkynes (not covered by the invention)

[0081] In addition to hydroamination, OH additions to alkynes can also be achieved. 4-Pentynoic acid reacts completely in THF at room temperature with 0.5 mol% YS PCy 2 ·AuCl and an equimolar amount of sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate to give the desired lactone within 14 h. C) Pd-catalyzed CN coupling reaction

[0082] The C–N coupling reaction of amines and haloaromatics was carried out according to known synthetic procedures with the respective ylide-substituted phosphines. The commercially available palladacycle di-µ-chlorobis[2'-(amino-N)[1,1'-biphenyl]-2-yl-C]dipalladium(II) was used as the palladium precursor and reacted with 1 equivalent of the phosphine ligand in THF. The amine and the bromo- or chloroaromatic were reacted with sodium tert-butoxide. Table 2: CN coupling of phenylaniline with aryl bromides and chlorides using the phosphine ligand Y Me PCy 2 . Approach catalyst; ligand = Amount of catalyst [mol%] Aryl halides Reaction time [h] Temperature [°C] Yield a< [%] 1 Y Me PCy 2 5 2-Bromotoluene 16 RT 99 2 Y Me PCy 2 5 4-chlorobenzonitriles 16 RT 40 3 Y Me PCy 2 5 4-chlorobenzonitriles 16 60 95 4 Y Me PCy 2 2.5 4-Chlorotoluene 18 100 17 5 Y Me PCy 2 2.5 4-Chlorotoluene 48 100 39 a) The yield was determined by NMR spectroscopy.

[0083] 1.5–2.0 equivalents of potassium tert-butoxide (or sodium tert-butoxide) were placed in a screw-cap vial in the glove box. Outside the glove box, the aryl chloride (0.9–1.2 mmol) and 1.1 eq. of an amine, as well as 2 mL of solvent, were added. A catalyst solution (see below) was prepared in a second vial, and the appropriate amount of catalyst was added to the reaction. The reaction mixture was stirred at room temperature. After the time specified in the table, the reaction was quenched with water, and the product was isolated by column chromatography. Alternatively, yields were determined by NMR spectroscopy. For p-fluorochlorobenzene, α,α,α-trifluorotoluene was used as the internal standard, and for the fluorine-free chloroaromatics, 1,3,5-trimethoxybenzene was used as the internal standard. For determinations after defined reaction times, small amounts of the reaction solution were withdrawn and quenched with a small amount of water.The organic phase was removed, filtered, and the solvent removed. The residue was dissolved in CDCl3, and the conversion was determined by the ratio of the product peaks to the internal standard.

[0084] In an analogous manner, aryl bromides can be used in the coupling reactions. Catalyst preparation:

[0085] 1) The ligand L1 (or L2-L6 ) and an equimolar amount of bis(dibenzylideneacetone)palladium(0) (or Pd(OAc)2) were dissolved in THF (or dioxane, or toluene; see table) and stirred for 30 minutes at room temperature. An appropriate amount of the solution was then added to the reaction vessel. 2) The precatalysts P1, P2, P4-P8 were dissolved in THF and stirred at room temperature for 30 minutes. An appropriate amount of the solution was then added to the reaction vessel. 3) The appropriate amount of precatalyst P3 was added directly to the reaction solution. Comparison of the catalytic activity of the ligands with known ligand systems

[0086] L1: R = Cy P4: L = RuPhos (L3) L3: R = Cy, R 1< ,R 3< = H, R 2< = O i Pr P8: PEPPSI-IPr L2: R = t This P5: L = BrettPhos (L4) L4: R = Cy, R 1< = OMe, R 2< ,R 3< = i Pr P6: L = JackiePhos (L5) L5: R = 3,5-(CF 3 ) 2 C 6 H 3 , R 1< = OMe, R 2< ,R 3< = R 2< ,R 3< = iPr P7: L = Ad 2 P( n (Bu) (L7) L6: R = t Bu, R 1< ,R 2< ,R 3< = H R (Pre)catalyst base solvent Yield [%] [a]< Me L1 ·Pd 2 dba 3 KOtBu THF 95 Me L1 ·Pd 2 dba 3 NaOtBu THF 52 Me L1 ·Pd 2 dba 3 KOtBu dioxane 99 F L1 ·Pd 2 dba 3 KOtBu THF 83 F L1 ·Pd 2 dba 3 NaOtBu THF 45 F L1 ·Pd 2 dba 3 KOtBu dioxane 88 F L1 ·Pd(OAc) 2 KOtBu THF 87 F P4 or P5 or P6 or P7 or P8 KOtBu THF <1 F L3 or L4 or L5 with Pd 2 dba 3 KOtBu THF <1 F L6 ·Pd(OAc) 2 [b]< NaOtBu toluene 10 (84) [c]< F L1 ·Pd(OAc) 2 [b]< NaOtBu toluene 78 (88) [c]< [a] Yields were determined by NMR spectroscopy. [b] 1 mol% ligand. [c] After 19 h. Application of various aryl chlorides with P* Me PCy 2 ( L1 ) as ligands

[0087]

[0088] Yields are isolated yields. Application of various amines and catalyst systems based on P* Me PCy 2 ( L1 ) and P* Me PtBu 2 ( L2 )

[0089] Catalyst: L1·Pd 2 dba 3

[0090] Catalyst: L2·Pd 2 dba 3

[0091] Catalyst: P2

[0092] Catalyst: P3

[0093] D) Pd-catalyzed CC coupling reaction

[0094] The CC coupling reaction of boronic acid and haloaromatics was carried out according to known synthetic procedures with the respective ylide-substituted phosphines. The commercially available palladacycle di-µ-chlorobis[2'-(amino-N)[1,1'-biphenyl]-2-yl-C]dipalladium(II) was used as the palladium precursor and reacted with one equivalent of the phosphine ligand in THF. The amine and the bromo- or chloroaromatic were reacted with an aqueous solution of potassium phosphate. Table 3: CC coupling of phenylboronic acid with aryl bromides and chlorides using the phosphine ligands Y Me PCy 2 and YsPCy 2 . Approach catalyst; ligand = Amount of catalyst [mol%] Aryl halides Reaction time [h] Temperature [°C] Yield a< [%] 1 YS PCy 2 2 2-Bromotoluene 24 RT 60 2 Y Me PCy 2 2 2-Bromotoluene 24 RT 16 3 Y Me PCy 2 5 2-Bromotoluene 24 60 99 4 Y Me PCy 2 2 4-Bromoacetophenone 48 RT 84 5 Y Me PCy 2 5 4-Chlorotoluene 24 60 27 6 Y Me PCy 2 5 4-chlorobenzonitriles 24 60 95 a) The yield was determined by NMR spectroscopy. Heck reaction with YPhos

[0095] Potassium carbonate was added to a Schlenk flask with a stir bar in a glove box. 2 ml of dry DMF (dimethylformamide), aryl halide (1, 1 mmol) and olefin (2, 1 mmol) were added.

[0096] A stock solution of catalyst and ligand was prepared by mixing 0.2 mmol of palladium acetate (Pd(OAc) 2 ) and 0.2 mmol of YPhos in a Schlenk tube. 1 mL of dry THF (tetrahydrofuran) was added and stirred for 30 min. 0.1 mL of the resulting solution was added to the reaction mixture and stirred for 3 h at 140 °C. Yields were determined by F NMR analysis using α,α,α-trifluorotoluene as an internal standard. YPhos:

[0097] 3a 22% (X=Br) 3b 22% (X=Br) 0% (X=Cl) 3c 0% (X=Br) 3d 0% (X=Br) Financial support

[0098] The project underlying this application has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (Grant Agreement No. 677749)

Claims

1. Metal complexes containing phosphane ligands of formulae (I) or (II) wherein On comprises a phosphonium group -P(R3R4R5) wherein R3, R4 and R5 are independently selected from the group consisting of C1-6 alkyl groups, C4-C10 cycloalkyl groups, C6-10 aryl groups, X1 is selected from the group consisting of straight chain, branched or cyclic C1-6 alkyl groups, C6-10 aryl groups, mono- or polyunsaturated, straight-chain, branched or cyclic C2-6 alkenyl groups, a trialkylsilyl-(-SiR3R4R5), arylsulfonyl group (R12SO2- with R12= C6-10 aryl) and R1 and R2 C6-10 aryl groups or C1-6 alkyl and cycloalkyl groups and wherein the metals platinum, palladium, copper, silver and nickel are used.

2. Metal complexes according to claim 1, wherein the metal palladium is used.

3. Metal complexes according to one or more of the preceding claims, wherein R3, R4 and R5 are independently selected from the group consisting of methyl, ethyl, butyl, cyclohexyl, phenyl and combinations thereof.

4. Metal complexes according to one or more of the preceding claims, wherein R3, R4 and R5 are the same and are selected from the group consisting of methyl, ethyl, butyl, cyclohexyl, phenyl and combinations thereof, in particular cyclohexyl and phenyl.

5. Metal complexes according to one or more of the preceding claims, wherein X1 is selected from the group consisting of methyl, ethyl, cyclohexyl, phenyl, p-tolyl, trimethylsilyl, p-tolylsulfonyl or combinations thereof.

6. Metal complexes according to one or more of the preceding claims, wherein R1 and R2 are independently selected from the group consisting of phenyl, cyclohexyl, methyl, tert.-butyl and combinations thereof.

7. Metal complexes according to claims 1 to 6, wherein the complex is a palladium-allyl complex of the following structure (V) or a palladium-aryl complex of structure (VI): mit where X is an anion, On, X1, Y, R1, R2, as defined in the preceding claims, R33, R34 and R35, are independently selected from H, alkyl, aryl and heteroaryl groups, which may be unsubstituted or substituted with functional groups; or at least two of R33, R34 and R35 can form a carbocyclic ring with 5 to 14 carbon atoms, Ar is a substituted or unsubstituted, in particular a substituted aryl group.

8. Metal complexes according to claim 7, wherein R33, R34 and R35 are independently selected from straight-chain, branched or cyclic C1-10 alkyl groups, preferably from C1-6 alkyl groups or C4-C10 cycloalkyl groups, the aryl groups are selected from C6-14 aryl groups, preferably from C6-10 aryl groups, the alkenyl groups are selected from mono- or polyunsaturated, straight-chain, branched or cyclic C2-10 alkenyl groups, preferably from C2-6 alkenyl groups, and the heteroaryl groups are selected from C6-14 heteroaryl groups, preferably from C6-10 heteroaryl groups, which have 1 to 5 hetero atoms selected from N, O and S, wherein the aforementioned groups may all be substituted with functional groups and / or at least two of R33, R34 and R35 form a carbocyclic ring which is a C4-C10 cycloalkyl group or a C6-14 aryl group which may be substituted by one or more functional groups, and Ar are selected from C6-14 aryl groups, preferably from C6-10 aryl groups, and the heteroaryl groups are selected from C6-14 heteroaryl groups, preferably from C6-10 heteroaryl groups, which have 1 to 5 heteroatoms selected from N, O and S, wherein the aforementioned groups may all be substituted with functional groups, and the functional groups are selected from alkyl (-R11), in particular C1-6 alkyl groups, C6-10 aryl (-R12), halogen (-Hal), hydroxy (-OH), cyano (-CN), alkoxy (-OR3), amino (-NR112, -NHR11, NH2), mercapto (-SH, -SR11), wherein R11, independently of further radicals R11, is selected from C1-6 alkyl radicals.

9. Metal complexes according to claim 11 or 12, wherein X is selected from the group consisting of halogen, tosylate, nosylate and mesylate.

10. Metal complexes according to one or more of the preceding claims, wherein X is selected from the group consisting of fluorine, chlorine, bromine, iodine, tosylate, nosylate and mesylate and / or aryl is selected from phenyl, m-tolyl, p-tolyl, o-tolyl, mesityl, 1,3-diisopropylphenyl.