DE102004006422A1 - Novel imidazolium and imidazolidinium salts can be used as precursors for carbene ligands for use in the preparation of novel metal complexes useful as catalysts - Google Patents

Abstract

Imidazolium and imidazolidinium salts are new, as are also metal complexes obtained from the salts. Imidazolium and imidazolidinium salts of formulae (Ia) and (Ib) are new. E : N, As or P; R1> and R2>H, optionally cyclic alkyl or optionally substituted aryl; R3> and R4>optionally cyclic alkyl or optionally substituted aryl; R5>as for R1> and R2> or a group of formula (R1>)'>-(E)'>:C((R2>)'>)-C((R3>)'>(R4>)'>)-; E'>as for E; (R1>)'> - (R4>)'>as for R1> - R4>; R6> and R7>H, optionally cyclic alkyl, optionally substituted aryl, halogen or nitro or together with the C atom to which they are bonded form a 4-10-membered ring which is optionally unsaturated and optionally contains 1 or 2 heteroatoms; X : an anionic group; and R8> and R9>H, optionally cyclic alkyl, optionally substituted aryl, halogen or nitro. Independent claims are also included for: (1) preparation of (Ia); (2) metal complexes which are derived from (Ia) and (Ib) and which are of formula (IIa) - (IIg); and (3) preparation of the metal complexes. R1> - R4> and R6> and R7>as above; R5>as for R1> and R2>; (R1>)''> - (R4>)''>as for R1> - R4>; E''>as for E; M : Group 3-13 metal; Y : monoanionic mono- or bi-dentate ligand; L : neutral mono- or bi-dentate ligand; n and m : 0-6, the ligands for n or m >= 1 being the same or different, n being such that the total Y charge corresponds to the valency of the metal and the sum n + m being dependent on the coordination numbers of the metals, the dentate values of Y and L and the number and dentate values of the functionalized carbene ligands; and the (R)' and (R)''> variables = as above. [Image] [Image] [Image] [Image].

Description

The Invention relates to novel imidazolium and imidazolidinium salts, the use of the imidazolium invention and imidazolidinium salts as precursors for functionalized carbene ligands for the preparation of metal complexes, metal complexes containing the corresponding carbene ligands, a process for the preparation of Metal complexes of the invention and the use of the metal complexes of the invention.

N-Heterocarbenverbindungen represent an interesting class of ligands for various metal complexes The resulting complexes can be used for a number of organic compounds Reactions can be used as catalysts, for example for C-C-, C-H and C-O linkages, as in W. Hermann, Angew. Chem. Int. 2002, 41, 1290 to 1309 is listed.

Of Furthermore, it is known from the prior art that, for example Imines or phosphines with different metals stable metal complexes form.

A Combination of several coordinating groups in one molecule leads to strong chelating ligands which have advantageous properties. In this context would be a combination of N-heterocarbene compounds with other ligands, for example imines or phosphines, to functionalized polydentate carbene compounds Interesting.

G. Bertrand et al., Chem. Rev. 2000, 100, 39 bis 91 gibt einen Überblick über stabile Carbene. Unter anderem sind Carbenkomplexe der Formeln

worin R = Me und L = PPh₃ oder R = CH₂CH₂OMe und L = PPh₃ oder R = CH₂CH₂OMe und L₂ = cis-COD bedeuten
und

worin R = Me und Ar = C₆Me₆ oder R = CH₂CH₂OMe und Ar = C₆Me₆ oder R = Me und Ar = Cymol oder R = CH₂CH₂OMe und Ar = Cymol bedeuten. Diese Komplexe werden in der Cyclopropanierung von Olefinen eingesetzt.WA Hermann et al., Angew. Chem. 1997, 109, 2256-2282 gives an overview of N-heterocyclic carbene compounds, their metal complexes and applications of metal complexes. Among others, functionalized chiral multidentate carbene compounds of the following formulas are described:

G. Bertrand et al., Chem. Rev. 2000, 100, 39-91 gives an overview of stable carbenes. Among others are carbene complexes of the formulas

where R = Me and L = PPh ₃ or R = CH ₂ CH ₂ OMe and L = PPh ₃ or R = CH ₂ CH ₂ OMe and L ₂ = cis-COD
and

where R = Me and Ar = C ₆ Me ₆ or R = CH ₂ CH ₂ OMe and Ar = C ₆ Me ₆ or R = Me and Ar = cymene or R = CH ₂ CH ₂ OMe and Ar = cymenol. These complexes are used in the cyclopropanation of olefins.

isoliert werden.AA Danopoulos et al., J. Chem. Soc., Dalton Trans., 2002, 3090-3091, relates to N-heterocyclic carbene complexes of iridium and rhodium having a pyridyl ligand. It can be a 5-ring chelate complex of the formula

be isolated.

According to S. P. Nolan et al., Organometallics 2001, 20, 2878-2882 are chiral nucleophilic carbene complexes. Among others, imidazoliden-2-ylidene ligands are disclosed, at their nitrogen atoms 2,4,6-trimethylphenyl or 2,6-Diisopropylreste wear.

K. J. Carvell et al., Organometallics 2000, 19, 741-748 Donor-functionalized palladium (II) carbene complexes and their use in C-C coupling reactions. The Pd complexes of the functionalized carbenes become silver-carbene complexes produced by carbene transfer. Functionalized imidazolium salts, having pyridine or carbonyl donor groups become neutral and cationic Pd complexes.

RE Douthwaite et al., Organometallics 2003, 22, 4187-4199 relates to chiral N-heterocyclic carbene-imine ligands and their application in Pd (II) -catalyzed asymmetric allylic alkylation reactions. The ligand precursor used is an imidazolium salt of the following formula:

These Ligands form carbene-imine metal complexes, with the imine double bond but not contained in the chelate ring, but outside the Chelatringes lies.

offenbart. Diese werden über Silber-Carbenkomplexe durch Carben-Transfer zu Pd- und Rh-Komplexen umgesetzt. In den Pd- und Rh-Chelatkomplexen liegt der Carben-Ligand jedoch nicht mehr als Carben-Imin-Ligand vor, sondern in Form des entsprechenden Enamin-Liganden, wie am Beispiel des Pd-Komplexes im folgenden dargestellt ist:

The synthesis of carbene-imine ligands and metal complexes having an imine functionality in the chelate ring obtainable therefrom is disclosed by KS Coleman et al., Dalton Trans., 2003, 2917-2922. These are imine-functionalized imidazolium salts of the formula

disclosed. These are converted via silver carbene complexes by carbene transfer to Pd and Rh complexes. However, in the Pd and Rh chelate complexes, the carbene ligand no longer exists as a carbene-imine ligand but in the form of the corresponding enamine ligand, as illustrated by the example of the Pd complex in the following:

task The present application therefore provides the provision of ligand precursors and Metal complexes, the ligand precursors corresponding ligands contained in the form of imino-carbene complexes or the corresponding P or As connections be present, wherein the imino-carbene ligand, or the corresponding Carbene ligand containing P or As, in the corresponding metal complex can form a 6-ring chelate complex with the central metal.

worin bedeuten:
in Formel Ia:
E N, As, P; R¹ Wasserstoff, ein linearer, verzweigter oder cyclischer Alkylrest, ein unsubstituierter oder substituierter Arylrest;
R² Wasserstoff, ein linearer, verzweigter oder cyclischer Alkylrest, ein unsubstituierter oder substituierter Arylrest;
R³, R⁴ unabhängig voneinander ein linearer, verzweigter oder cyclischer Alkylrest, ein unsubstituierter oder substituierter Arylrest;
R⁵ Wasserstoff, ein linearer, verzweigter oder cyclischer Alkylrest, ein unsubstituierter Arylrest oder ein Rest der Formel

worin R¹', R²', R³' und R⁴' die für R¹, R², R³ und R⁴ genannten Bedeutungen aufweisen;
R⁶, R⁷ unabhängig voneinander Wasserstoff, ein linearer, verzweigter oder cyclischer Alkylrest, ein unsubstituierter oder substituierter Arylrest, Halogen oder eine Nitrogruppe
oder
R⁶ und R⁷ bilden gemeinsam mit den Kohlenstoffatomen, an die sie gebunden sind, einen 4- bis 10-gliedrigen Ring, der gesättigt oder ungesättigt sein kann und gegebenenfalls ein oder zwei Heteroatome, bevorzugt N, aufweisen kann;
X^– ein anionischer Rest;
und
in Formel Ib bedeuten:
E, E', R¹, R², R³, R⁴, R⁵, R¹', R²', R³', R⁴', R⁶, R⁷ und X^– die bezüglich Formel Ia genannten Bedeutungen, und
R⁸, R⁹ unabhängig voneinander Wasserstoff, ein linearer, verzweigter oder cyclischer Alkylrest, ein unsubstituierter oder substituierter Arylrest, Halogen oder eine Nitrogruppe.This object is achieved by the provision of compounds of the general formulas Ia or Ib

in which mean:
in formula Ia:
EN, As, P; R ^{1 is} hydrogen, a linear, branched or cyclic alkyl radical, an unsubstituted or substituted aryl radical;
R ^{2 is} hydrogen, a linear, branched or cyclic alkyl radical, an unsubstituted or substituted aryl radical;
R ³ , R ⁴ independently of one another are a linear, branched or cyclic alkyl radical, an unsubstituted or substituted aryl radical;
R ^{5 is} hydrogen, a linear, branched or cyclic alkyl radical, an unsubstituted aryl radical or a radical of the formula

wherein R ¹ ', R ² ', R ³ 'and R ⁴ ' have the meanings given for R ¹ , R ² , R ³ and R ⁴ ;
R ⁶ , R ⁷ independently of one another are hydrogen, a linear, branched or cyclic alkyl radical, an unsubstituted or substituted aryl radical, halogen or a nitro group
or
R ⁶ and R ⁷ together with the carbon atoms to which they are attached form a 4- to 10-membered ring which may be saturated or unsaturated and may optionally have one or two heteroatoms, preferably N;
X ^- an anionic radical;
and
in formula Ib mean:
E, E ', R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ¹ ', R ² ', R ³ ', R ⁴ ', R ⁶ , R ⁷ and X ^- the meanings given with respect to formula Ia , and
R ⁸ , R ⁹ independently of one another are hydrogen, a linear, branched or cyclic alkyl radical, an unsubstituted or substituted aryl radical, halogen or a nitro group.

The Compounds of formulas Ia and Ib are characterized in that the functionalities of N-heterocarbene compounds and chelating ligands, the carry a nitrogen, phosphorus or As atom, unite. Thereby can the advantageous properties of the N-heterocarbene complexes with the containing advantageous properties of coordinating groups N, P or As can be combined. Such ligands are therefore suitable in particular for the preparation of metal complexes of these ligands, the diverse, for example, as catalysts, can be used.

darstellt, so weisen die erfindungsgemäßen Verbindungen die Formeln Ic oder Id auf:

worin die Reste R¹, R², R³, R⁴, R⁵, R¹', R²', R³', R⁴', R⁶, R⁷, X^–, E' und E die vorstehend genannten Bedeutungen aufweisen.When R ^{5 is} a radical of the formula

represents, the compounds of the invention have the formulas Ic or Id:

wherein the radicals R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ¹ ', R ² ', R ³ ', R ⁴ ', R ⁶ , R ⁷ , X ^- , E 'and E are those mentioned above Have meanings.

It was found to be due to incorporation of a quaternary carbon atom in the α position to the group C = E or C = E 'stable ligand precursor and metal complexes can be prepared, with no tautomerism the group C = E or C = E 'occurs, like you, according to Coleman et al. is observed. In this way, metal complexes are accessible, wherein the central metal has a 6-membered chelate complex with an imino carbene ligand or form a corresponding P- or As-containing carbene ligands may, wherein the imine double bond or the corresponding double bond to P or As contained in the chelate ring.

Under a bidentate ligand is understood as meaning a ligand attached to two Sites to the metal atom M is coordinated. In the sense of the present Application, the term "bidentate" synonymous with the Term "bidentate" used.

Under a monodentate ligand is understood to be a ligand attached to a site of the ligand coordinated with the metal atom M.

In a preferred embodiment In the present invention, E and optionally E 'N are preferred compounds of the formulas Ia and Ic are thus imino-functionalized imidazolium salts and preferred compounds of formulas Ib and Id are imino-functionalized Imidazolidiniumsalze. These are precursors for multiply coordinating phosphorus and sulfur-free ligands suitable for transition metal complexes. The freedom from phosphorus of the preferred ligand precursors according to the invention and the metal complexes prepared therefrom is advantageous since phosphorus-containing Ligands in metal complexes often lead to problems in the recovery of metals.

suitable linear or branched alkyl radicals are alkyl radicals having 1 to 30 Carbon atoms, preferably 1 to 20 carbon atoms, such as methyl, Ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl and n-hexyl.

suitable cyclic alkyl radicals are cyclic saturated carbon radicals 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and adamantyl.

suitable Aryl radicals are those having 6 to 30 carbon atoms, preferred 6 to 20 carbon atoms, such as phenyl, benzyl, naphthyl, biphenyl, Terphenyl, phenanthryl and anthracenyl. The aryl radicals may further be alkyl-substituted. Suitable alkyl-substituted aryl radicals are Tolyl, isopropylphenyl, tert-butylphenyl, dimethylphenyl and di-tert-butylphenyl.

In The above-mentioned alkyl and aryl radicals may have one or more hydrogen atoms by halogen atoms, oxygen-containing groups such as ester groups or ether groups, nitrogen-containing groups such as amide groups or Replaced amino groups or sulfur-containing groups such as thio groups be. Examples of halogenated Alkyl and aryl radicals are trifluoromethyl, pentafluorophenyl and Chlorophenyl.

Of Furthermore, it is possible in the abovementioned alkyl and aryl radicals, an or several hydrogen atoms through hydrocarbon radicals, for example further alkyl or aryl radicals, alkyl-substituted aryl radicals or Aryl-substituted alkyl radicals such as benzyl and cumyl, are replaced.

R ⁶ and R ⁷ may further together with the carbon atoms to which they are attached form a 4- to 10-membered ring which may be saturated or unsaturated. R ⁶ and R ⁷ together with the carbon atoms to which they are attached preferably form a 6-membered ring, which is particularly preferably unsaturated and very particularly preferably represents a phenylene radical. This may in turn be substituted with alkyl or aryl radicals as defined above.

R ⁶ and R ⁷ in the compounds of the formulas Ia, Ib, Ic and Id and R ⁸ and R ⁹ in the compound of the formulas Ib and Id are independently of one another hydrogen, halogen, a nitro group or linear or branched alkyl radicals having 1 to 20 Carbon atoms such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, neo-pentyl and n-hexyl, most preferably having 1 to 10 carbon atoms, and particularly preferably with 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl. Furthermore, R ⁶ and R ⁷ and R ⁸ and R ⁹ are each independently aryl radicals having 6 to 20 carbon atoms, such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl and anthracenyl, which may be substituted by alkyl groups, very particularly preferably phenyl, naphthyl, Tolyl and cumyl.

R ¹ , R ² and R ⁵ are preferably, independently of one another, hydrogen, linear or branched alkyl radicals having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl Butyl, neo-pentyl and n-hexyl, most preferably having 1 to 10 carbon atoms and particularly preferably having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl. Furthermore, R ¹ , R ² and R ⁵ are preferably aryl radicals having 6 to 20 carbon atoms, such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl and anthracenyl, which may be substituted by alkyl groups, very particularly preferably phenyl, naphthyl, tolyl and cumyl.

sein, wobei bevorzugte Reste R¹', R²', R³' und R⁴' den bevorzugten Resten R¹, R², R³ und R⁴ unabhängig von diesen entsprechen. Bevorzugte Gruppen E' sind bereits vorstehend genannt.Furthermore, R ⁵ may be a radical of the formula

where preferred radicals R ¹ ', R ² ', R ³ 'and R ⁴ ' correspond to the preferred radicals R ¹ , R ² , R ³ and R ⁴ independently of these. Preferred groups E 'are already mentioned above.

X ^- is generally halide, preferably Cl ^- or Br ^- , pseudohalide, preferably CN ^- , carboxylate, triflate, OH ^- , OR '' ^- , wherein R "is generally an alkyl or aryl radical as defined above, preferably a C ₁ - to C ₄ alkyl, for example methyl, ethyl, i-propyl or tert-butyl.

R ³ and R ⁴ are preferably linear or branched alkyl radicals having 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, neo-pentyl and n -Hexyl, particularly preferably having 1 to 10 carbon atoms such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl, most preferably having 2 to 10 carbon atoms, and particularly preferred with 2 to 4 carbon atoms such as ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl. Furthermore, R ³ and R ⁴ are preferably, independently of one another, phenyl, tolyl or cumyl.

The Compounds of the formulas Ia and Ib as well as Ic and Id can be used according to any method, analogous to the method known to those skilled in the art, getting produced.

The compounds of the invention (imidazolium salts) of the formulas Ia and Ic can be reacted, for example, by reacting potassium imidazolide or a derivative thereof with a first equivalent of a corresponding alkyl halide to give a 1-alkylimidazole or a derivative thereof. Subsequent alkylation in the 3-position is achieved by addition of another equivalent of a suitable alkyl halide. In a variant of this method of preparation, commercially available N-trimethylsilylimidazole or a derivative thereof is prepared with two equivalents of a suitable alkyl chloride with elimination of volatile Me ₃ SiCl.

wobei R⁶ und R⁷ bereits vorstehend definiert wurden, und Formaldehyd in Anwesenheit einer Säure.Furthermore, the imidazolium salts of the formulas Ia and Ic can be prepared by reacting suitable primary amines with a 1,2-dicarbonyl compound of the formula

wherein R ⁶ and R ^{7 have} already been defined above, and formaldehyde in the presence of an acid.

Of Furthermore, it is possible to perform a combination of the above methods, wherein 1-Alkylimidazole starting from 1,2-dicarbonyl compounds of the above formula, formaldehyde, a suitable amine and ammonium chloride produced and then by alkylation with a primary Alkyl halide are reacted. This creates the desired Imidazolium.

Farther is the direct coupling of imidazoles and derivatives thereof suitable aryl iodides in the presence of copper (I) triflate possible, wherein 1-arylimidazoles are obtained. These can be done in a second step be alkylated as mentioned above.

The corresponding benzimidazolium salts of the formulas Ia or Ic in which R ⁶ and R ⁷ together with the carbon atoms to which they are attached form a phenylene radical can be obtained, for example, by abstraction of a hydride from 2,3-dihydro-1-H-benzimidazoles with tritylium tetrafluoroborate getting produced.

The The above mentioned processes are described in W.A. Hermann, Advances in Organometallic Chemistry, Volume 48, pages 1 to 69 and therein disclosed literature.

• i) Umsetzung von Imidazol oder einem Derivat davon mit einer Carbonylverbindung der Formel VII zu einer Carbonylverbindung der Formel IIIa
  
  Hal = Halogen, bevorzugt Cl oder Br;
• ii) anschließende Umsetzung der Carbonylverbindung der Formel IIIa mit einer Verbindung der Formel IV, bevorzugt einem Amin, wobei eine Verbindung der Formel Va gebildet wird
  
• iii) Umsetzung der Verbindung der Formel Va mit einem Salz der Formel VI zu der gewünschten Verbindung der Formel Ia oder Ic
  

In a further embodiment of the present invention, the preparation of Verbindun (Imidazoliumsalzen) of the formulas Ia and Ic by the following steps:

• i) reacting imidazole or a derivative thereof with a carbonyl compound of the formula VII to give a carbonyl compound of the formula IIIa
  
  Hal = halogen, preferably Cl or Br;
• ii) subsequent reaction of the carbonyl compound of the formula IIIa with a compound of the formula IV, preferably an amine, forming a compound of the formula Va
  
• iii) reaction of the compound of the formula Va with a salt of the formula VI to give the desired compound of the formula Ia or Ic
  

The meanings of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , E and X have already been mentioned above.

In an alternative process for the preparation of the compounds of Formulas Ia or Ic takes place first a reaction of the carbonyl compound of formula VII with a compound of formula IV, preferably an amine, (step (i ')) and subsequent reaction of the obtained Compound with imidazole or a derivative thereof, wherein a compound of the formula Va is formed (step (ii ')). The desired compound of the formula Ia or Ic will follow by reacting the compound of formula Va with a salt of the formula VI received, according to step iii) the above method. The reaction conditions the first two steps correspond to the step i) and step ii) of the aforementioned method Reaction conditions, the reaction conditions of step i) the above method, the reaction conditions from step ii ') and the reaction conditions of step ii) of the above said method correspond to the reaction conditions of step i ').

Step i)

step i) is generally in solution carried out. Suitable solvents are alcohols such as methanol, ethanol and isopropanol and aromatic Hydrocarbons such as toluene, preferably ethanol.

Usually in step i) imidazole or a derivative thereof in a solvent submitted and the corresponding carbonyl compound of the formula VII added.

The reaction solution is heated to generally -10 to 180 ° C, preferably 30 to 150 ° C, particularly preferably 40 to 100 ° C. The reaction mixture is allowed to react for a period of 20 minutes to 10 days, preferably maintained at said temperature for 12 hours to 24 hours. Subsequently, the reaction mixture is cooled and worked up by methods known to those skilled in the art.

imidazole or a derivative thereof and the carbonyl compound of the formula VII are generally added in a molar ratio of 10 to 1 to 1 1, preferably used 2.5 to 1 to 2 to 1.

The used as starting materials carbonyl compounds and imidazole and its derivatives can be prepared by methods known to those skilled in the art and partially commercially available.

Step ii)

In the subsequent step ii), the resulting carbonyl compound of the formula IIIa is reacted with a compound of the formula R ¹ -EH ₂ (formula IV). The reaction preferably takes place with a primary amino compound of the general formula R ¹ -NH ₂ .

Basically all processes for the preparation of imino compounds or the corresponding P or As containing compounds known to those skilled in the art, suitable for the preparation of the compound of formula Va.

Preferably, the compound of formula IV, more preferably the amine, is first activated with the aid of a Lewis acid, preferably Al (CH ₃ ) ₃ . This activation generally takes place in a solvent, for example in toluene. For activation, the reaction mixture is heated to generally 30 to 120 ° C, preferably 50 to 100 ° C and for generally 1 hour to 3 days, preferably 1 hour to 10 hours.

To the solution the activated compound of formula IV becomes the carbonyl compound given the formula IIIa. The reaction mixture is at a temperature from generally 20 to 150 ° C, preferably 50 to 100 ° C for one Period of generally 1 hour to 3 days, preferably 1 hour up to 24 hours.

The The reaction mixture obtained is known in the art worked up. Preferably, the reaction mixture is cooled to 0 ° C and carefully quenched with ice. The further work-up is carried out according to customary Methods, for example by adding methylene chloride and subsequent washing the organic phase first with an aqueous NaOH solution and subsequently with water and drying over a suitable drying agent and subsequent removal of the solvent. A Cleaning the desired Product of formula Va can be carried out by chromatography.

The Compound of the formula IV and the carbonyl compound of the formula IIIa be in a molar ratio of generally 2 to 1 to 1 to 2, preferably 1 to 1 used.

Step iii)

The The resulting compound of formula Va is then converted into the desired imidazolium salt of the formula Ia or Ic. This is generally done by loosening the compound of formula Va, for example in methylene chloride, and subsequent Cooling the solution on generally -120 to -10 ° C, preferably -100 to -60 ° C.

To the resulting solution is added a suitable salt R ⁵ -X (formula VI), in particular a suitable triflate. Subsequently, stirring is first carried out at the abovementioned temperature for a period of generally 0.5 hours to 8 hours, preferably 1 hour to 6 hours. Thereafter, it is generally heated to 20 to 25 ° C and further stirred at 20 to 25 ° C for a period of generally 0.5 hours to 8 hours, preferably 1 hour to 6 hours. Finally, the solvent is removed in vacuo and the residue is worked up according to methods known to those skilled in the art, for example by washing with diethyl ether and subsequent drying.

The Compound of formula Va is in a molar ratio to the salt of formula VI of generally 2 to 1 to 1 to 2, preferably 0.9 to 1.1 to 1.1 to 0.9.

The imidazolidinium salts of the formulas Ib or Id can be prepared by processes known to those skilled in the art. For example, the compounds of formulas Ib or Id are possible by reaction of a suitable ortho-ester, for example HC (OEt) ₃ , with a suitable secondary bisamine in the presence of an ammonium salt to obtain the corresponding imidazolidinium salts. The secondary diamines can be obtained by a classical condensation reduction or by palladium-catalyzed Buchwald-Hartwig amination. Suitable processes for the preparation of imidazolidinium salts of the formulas Ib or Id are disclosed, for example, in WA Hermann, Advances in Organometallic Chemistry, Volume 48, pages 1 to 69 and the literature cited therein.

The according to the invention imidazolium or imidazolidinium salts of the formulas Ia or Ic and Ib or Id are suitable himself as a forerunner for functionalized Carbene ligands for the preparation of metal complexes. These metal complexes are diverse can be used as catalytic compounds in numerous reactions.

worin die Reste R¹, R², R³, R⁴, R⁵, R⁶, R⁷ und E in den Formeln VIIIa und VIIIb sowie die Reste R⁸ und R⁹ in Formel VIIIb die vorstehend genannten Bedeutungen aufweisen.The functionalized carbene complexes generally have the following general formulas VIIIa and VIIIb:

wherein the radicals R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and E in the formulas VIIIa and VIIIb and the radicals R ⁸ and R ⁹ in formula VIIIb have the meanings given above.

darstellt, so weisen die erfindungsgemäßen Verbindungen die Formeln VIIIc oder VIIId auf:

worin die Reste R¹, R², R³, R⁴, R⁵, R¹', R²', R³', R⁴', R⁶, R⁷, X^–, E' und E die vorstehend genannten Bedeutungen aufweisen.When R ^{5 is} a radical of the formula

represents, the compounds of the invention have the formulas VIIIc or VIIId:

wherein the radicals R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ¹ ', R ² ', R ³ ', R ⁴ ', R ⁶ , R ⁷ , X ^- , E 'and E are those mentioned above Have meanings.

The Compounds of the formulas VIIIa, VIIIb, VIIIc and VIIId can be described as functionalized carbene ligands are used in metal complexes. The carbene compounds of the formulas VIIIa, VIIIb, VIIIc and VIIId can be prepared analogously to methods known in the art. she are used e.g. by deprotonation of the corresponding imidazolium or imidazolidinium complexes of the formulas Ia, Ib, Ic or Id.

One Another object of the present application is therefore the use of compounds of the formulas Ia or Ib, where the compounds of the formula Ic of the formula Ia and the compounds the formula Id of the formula Ib, as a precursor for functionalized carbene ligands for the preparation of metal complexes.

The characterized functionalized carbene ligands containing metal complexes through a combination of the properties of carbene complexes with the properties of imine complexes or the corresponding P or As containing complexes.

worin bedeuten:
in den Formeln IIa und IIc
E N, As, P;
R¹ Wasserstoff, ein linearer, verzweigter oder cyclischer Alkylrest, ein unsubstituierter oder substituierter Arylrest;
R² Wasserstoff, ein linearer, verzweigter oder cyclischer Alkylrest, ein unsubstituierter oder substituierter Arylrest;
R³, R⁴ unabhängig voneinander ein linearer, verzweigter oder cyclischer Alkylrest, ein unsubstituierter oder substituierter Arylrest;
R⁵ Wasserstoff, ein linearer, verzweigter oder cyclischer Alkylrest, ein unsubstituierter oder substituierter Arylrest;
R⁶, R⁷ unabhängig voneinander Wasserstoff, ein linearer, verzweigter oder cyclischer Alkylrest, ein unsubstituierter oder substituierter Arylrest, Halogen oder eine Nitrogruppe,
oder
R⁶ und R⁷ bilden gemeinsam mit den Kohlenstoffatomen, an die sie gebunden sind, einen 4- bis 10-gliedrigen cyclischen Rest, der gesättigt oder ungesättigt sein kann und gegebenenfalls ein oder zwei Heteroatome, bevorzugt N, aufweisen kann;
M Metallatom der Gruppe 3 bis 13 des Periodensystems der Elemente;
Y monoanionischer Ligand, der mono- oder bidentat sein kann;
L neutraler mono- oder bidentater Ligand;
n Zahl der Liganden Y von 0 bis 6, wobei die Liganden Y bei n > 1 gleich oder verschieden sein können;
m Zahl der Liganden L von 0 bis 6, wobei die Liganden L bei m > 1 gleich oder verschieden sein können;
wobei n so gewählt wird, dass die Ladung aller Liganden Y der Wertigkeit des eingesetzten Metallatoms entspricht, und die Summe aus n und m von der Koordinationszahl des eingesetzten Metallatoms und der Zähnigkeit der Liganden Y und L und der Zähnigkeit des eingesetzten funktionalisierten Carbenliganden abhängig ist;
und
in den Formeln IIb und IId bedeuten
E, E', R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R¹', R²', R³', R⁴', M, Y, L, n und m die bezüglich der Formel IIa und IIc genannten Bedeutungen, und
R⁸, R⁹ unabhängig voneinander Wasserstoff, ein linearer, verzweigter oder cyclischer Alkylrest, ein unsubstituierter oder substituierter Arylrest, Halogen oder eine Nitrogruppe.Another object of the present application are metal complexes of the general formulas IIa, IIb, IIc or IId

in which mean:
in formulas IIa and IIc
EN, As, P;
R ^{1 is} hydrogen, a linear, branched or cyclic alkyl radical, an unsubstituted or substituted aryl radical;
R ^{2 is} hydrogen, a linear, branched or cyclic alkyl radical, an unsubstituted or substituted aryl radical;
R ³ , R ⁴ independently of one another are a linear, branched or cyclic alkyl radical, an unsubstituted or substituted aryl radical;
R ^{5 is} hydrogen, a linear, branched or cyclic alkyl radical, an unsubstituted or substituted aryl radical;
R ⁶ , R ⁷ independently of one another are hydrogen, a linear, branched or cyclic alkyl radical, an unsubstituted or substituted aryl radical, halogen or a nitro group,
or
R ⁶ and R ⁷ together with the carbon atoms to which they are attached form a 4- to 10-membered cyclic radical which may be saturated or unsaturated and may optionally have one or two heteroatoms, preferably N;
M metal atom of Group 3 to 13 of the Periodic Table of the Elements;
Y monoanionic ligand, which may be mono- or bidentate;
L neutral mono- or bidentate ligand;
n number of ligands Y from 0 to 6, where the ligands Y may be the same or different at n>1;
m number of ligands L from 0 to 6, wherein the ligands L may be the same or different at m>1;
where n is chosen such that the charge of all ligands Y corresponds to the valency of the metal atom used, and the sum of n and m depends on the coordination number of the metal atom used and the denticity of the ligands Y and L and the denticity of the functionalized carbene ligand used;
and
in the formulas IIb and IId
E, E ', R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ¹ ', R ² ', R ³ ', R ⁴ ', M, Y, L, n and m is the meanings given with respect to formulas IIa and IIc, and
R ⁸ , R ⁹ independently of one another are hydrogen, a linear, branched or cyclic alkyl radical, an unsubstituted or substituted aryl radical, halogen or a nitro group.

Preferred definitions of the groups E, E ', R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ¹ ', R ² ', R ³ ', R ⁴ ', R ⁸ and R ⁹ are already mentioned above.

M is preferably selected from the group consisting of Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Ti, Zr, V, Mn, Sc, Cr, Mo, W, Fe, Cu, Ag and Al, particularly preferred Ni, Pd, Ru, Os, Cu, Rh, Ir, Pt, Ti, Zr, V, Mn, Fe and Sc.

Suitable monoanionic ligands Y can be mono- or bidentate. The monoanionic ligands Y are preferably selected from the group consisting of halides, in particular Cl ^- and Br ^-, pseudohalides, in particular CN ^-, cyclopentadienyl (Cp), the cyclopentadienyl groups having alkyl substituents, preferably methyl or tert-butyl, can be substituted, particularly preferably having five methyl groups, such that the substituted cyclopentadienyl radical is pentamethylcyclopentadienyl (Cp *), indenyl, where the indenyl radical may optionally be substituted by alkyl substituents, preferably methyl, alkyl radicals which are linked to the metal atom M via a sigma bond, for example CH ₃ , alkylaryl groups linked to the metal atom M via a sigma bond, for example benzyl, alcoholates, for example OCHS, trifluorosulfonates, carboxylates, carbenes, acetylacetonate and its derivatives, the anion of picolinic acid and anions of amino acids. Preferably, the ligand Y is selected from the group consisting of halides, alcoholates, carboxylates, acetylacetonate and its derivatives, trifluorosulfonate, carbene, indenyl, pentamethylcyclopentadienyl and cyclopentadienyl.

Suitable neutral mono- or bidentate ligands L are preferably selected from the group consisting of amines, ethers, water, alcohols, carbon monoxide, nitriles, in particular alkylnitriles, pyridines, where the pyridines may be substituted by alkyl or aryl groups, phosphines, preferably trialkyl , Triaryl or alkylarylphosphines, particularly preferably PAr ₃ , where Ar is a substituted or unsubstituted aryl radical and the three aryl radicals in PAr _{3 may be} identical or different, particularly preferably PPh ₃ , PEt ₃ , PnBu ₃ , PEt ₂ Ph, PMe ₂ Ph, PnBu ₂ Ph, phosphonates and derivatives thereof, arsenates and derivatives thereof, phosphites, conjugated dienes which form an n-complex with the metal atom M, preferably η ⁴ -1,3-butadiene, η ⁴ -diphenyl-1,3 -butadiene, η ⁴ -1,3-pentadiene, η ⁴ -1-phenyl-1,3-pentadiene, η ⁴ -1,4-dibenzyl-1,3-butadiene, η ⁴ -2,4-hexadiene, η ⁴ -3-methyl-1,3-pentadiene, η ⁴ -1,4-ditolyl-1,3-butadiene, η ⁴ -1,4-bis (trimethylsilyl) -1,3-butadiene and η ² - or η ⁴ -cyclooctadiene (COD) (each 1.3 and 1.5 each), more preferably η ⁴ -1,4-diphenyl-1,3-butadiene, η ⁴ -1-phenyl-1, 3-pentadiene, η ⁴ -2,4-hexadiene, butadiene, η ⁴ -1,3-cyclooctadiene and η ⁴ -1,5-cyclooctadiene, and multiple bond acetylenic unsaturation systems.

Phosphorus-free ligands used as neutral mono- or bidentate ligands are preferably selected from the group consisting of amines, ethers, water, alcohols, pyridines, where the pyridines may be substituted by alkyl or aryl groups, carbon monoxide, nitriles, preferably alkylnitriles, η ⁴ -1,4-diphenyl-1,3-butadiene, η ⁴ -1-phenyl-1,3-pentadiene, η ⁴ -2,4-hexadiene, η ⁴ -cyclooctadiene and η ² -cyclooctadiene (each 1.3 and 1.5 each).

worin R¹, R², R³, R⁴, R⁵, R⁶, R⁷, E, Y, L, m und n in den Formeln IIe, IIf und IIg sowie R⁸, R⁹ in den Formeln IIf und IIg bereits vorstehend definiert wurden und R^1'' R^2'' R^3'', R^4'', R^5', R^6', R^7', R^8', R^9' und E'' unabhängig die für R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ und E genannten Bedeutungen aufwiesen. M ist ein Metallatom, ausgewählt aus den vorstehend für M genannten Metallatomen, das eine Koordinationszahl von mindestens 4 aufweist.Another object of the present application are metal complexes having two functionalized carbene ligands of the general formulas IIe, IIf or IIg

wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , E, Y, L, m and n in the formulas IIe, IIf and IIg and R ⁸ , R ⁹ in the formulas IIf and IIg have already been defined above and R ^{1 "} R ^2" R ^{3 "} , R ^4" , R ^{5 '} , R ^6' , R ^{7 '} , R ^8' , R ^{9 '} and E "independently of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and E have meanings mentioned. M is a metal atom selected from the metal atoms mentioned above for M, which has a coordination number of at least 4.

suitable Metal complexes are, for example, metal complexes of the general Formulas IIa or IIb, wherein Pd is used as metal atom. Prefers is in the Pd complexes of the formulas IIa or IIb Y is a monoanionic monodentate ligand, especially preferred is chloride. The number of monoanionic monodentates Ligand Y in the Pd complex of formula IIa or IIb is particularly preferably 2 and the number of neutral mono- or bidentate ligands L is more preferably 0.

Some examples of suitable Pd complexes of the formulas IIa or IIb are listed below

Furthermore, Pd complexes of the formulas IIa or IIb are suitable, wherein Y is preferably a monoanionic monodentate ligand, more preferably chloride, and the number n of ligands Y is 1. Such Pd complexes are exemplified below:

R = Wasserstoff, Alkylrest, ArylrestFurthermore, metal complexes of the general formulas IIe, IIf and IIg, for example Pd complexes, which carry two functionalized carbene ligands are suitable. In the case of Pd complexes, such metal complexes bearing two functionalized carbene ligands contain no other ligands Y or L, that is, n and m are 0. Suitable Pd complexes bearing two functionalized carbene ligands are listed below:

R = hydrogen, alkyl radical, aryl radical

Becomes used as the metal atom Ru, compounds of the formulas IIa and IIb in which Y is a monoanionic monodentate ligand, for example halide or a carbene ligand. The number of monoanionic monodentate ligand Y is in the Ru complexes of the formulas IIa or IIb preferred 3.

Suitable Ru complexes of the formulas IIa or IIb are listed below:

R = Wasserstoff, Alkylrest, ArylrestSuitable Ru complexes of the formulas IIc or IId preferably contain further monoanionic monodentate ligands Y, particularly preferably chloride. The number of monoanionic monodentate ligands Y in the Ru complexes of the formulas IIc or IId is particularly preferably 2. Suitable Ru complexes of the formulas IIc or IId are listed below:

R = hydrogen, alkyl radical, aryl radical

R' = anionischer Ligand, bevorzugt Cyclopentadienyl, Pentamethylcyclopentadienyl, IndenylSuitable Ir or Rh complexes of the formulas IIa or IIb generally have, in addition to the functionalized carbene ligand, a further ligand Y, which is preferably monoanionic and monodentate. Suitable anionic ligands are cyclopentadienyl wherein all five hydrogen atoms may be substituted by methyl radicals, as well as indenyl. The number n of the ligands Y in the Ir and Rh complexes of the formulas IIa or IIb is preferably 1. Suitable Ir and Rh complexes of the formulas IIa or IIb are listed below:

R '= anionic ligand, preferably cyclopentadienyl, pentamethylcyclopentadienyl, indenyl

In the case where the metal atom M denotes Ni, preferred metal complexes of the formulas IIa or IIb have a functionalized carbene ligand. Furthermore, the Ni complexes of the formulas IIa or IIb preferably contain monoanionic monodentate ligands Y, particularly preferably chloride. The number n of the ligands Y is preferably 2. Suitable Ni complexes of the formulas IIa or IIb are listed below:

Further, the metal atom M may be W, for example. Suitable W complexes of the formulas IIa or IIb have, for example, a functionalized carbene ligand. Furthermore, these complexes preferably contain neutral monodentate ligands, more preferably CO. Most preferably, the number m of the neutral monodentate ligands is 4, while the number n of the monoanionic ligands Y is 0. A suitable W complex of formula IIa is shown below:

The Metal complexes according to the present invention Registration can be prepared analogously to methods known in the art. suitable Particularly preferred methods of preparation are the deprotonation of ligand precursors in situ, the complexation of free, isolated functionalized Carbene ligands and the cleavage of electron-rich olefins by means Metal complexes. Suitable manufacturing methods are, for example in W.A. Hermann et al., Advances in Organometallic Chemistry, Volume 48, pages 1 to 69 and the literature cited therein.

Prefers the preparation of the metal complexes according to the invention is carried out by deprotonation of ligand precursors, preferably in situ.

One Another object of the present application is therefore a method for the preparation of the metal complexes of the formulas according to the invention IIa, IIb, IIc or IId by deprotonation of corresponding ligand precursors according to the formulas Ia, Ib, Ic or Id and subsequent Implementation with a metal complex. Metal complexes of formulas IIe, IIf and IIg are produced by a similar process, with the molar proportion of precursors the functionalized carbene ligands of the formulas IIa, IIb, IIc or IId opposite the production process of the metal complexes of the formulas IIa, IIb, IIc or IId is twice as high.

The Deprotonation of the imidazolium or imidazolidinium salts according to the formulas Ia or Ib (or Ic or Id, the ligand precursors of the Formulas Ic and Id of the formulas Ia and Ib are included, so in the following, only the ligand precursors of the formulas Ia and Ib called) is generally carried out by means of basic anions. It will be the desired functionalized carbene ligand formed in situ by deprotonation. Suitable basic anions are, for example, metal acetates, acetylacetonates or alkoxylates or metal hydrides, for example potassium hydride.

The Deprotonation is generally carried out in a solvent, preferably in one polar aprotic solvents, for example tetrahydrofuran. Generally done the deprotonation at a temperature of 0 to 100 ° C, preferably 20 to 40 ° C. The reaction time is generally 1 hour to 2 days, preferably 1 hour to 6 hours.

through Deprotonation generally becomes the desired functionalized carbene ligand obtained in situ. This one comes with a suitable metal complex to the desired Metal complex of formula IIa or IIb implemented (metallation). The metalation is generally carried out by adding the corresponding metal complexes to the reaction mixture obtained after deprotonation.

Suitable metal complexes are, for example, PdCl ₂ , PdCl ₂ (PPh ₃ ) ₂ , allyl palladium chloride, tris (dibenzylideneacetone) dipalladium, Pd (CH ₃ CN) ₄ (BF ₄ ) ₂ , NiCl ₂ , NiBr ₂ (dimethoxyethane), bis (1 , 5-cyclooctadiene) nickel, NiCl ₂ (PPh ₃ ) ₂ , bis (1,5-cyclooctadiene) rhodium, acetylacetonate bis (ethylene) rhodium, RhCl ₃ , Ir (acetylacetonate) ₃ , PtCl ₂ , PtCl ₄ , Bis ( 1,5-cyclooctadiene) platinum, TiCl ₃ , TiCl ₄ , Ti (Oi-propyl) ₄ , ZrCl ₄ , tetrakis (dimethylamino) zirconium, osmium carbonyl, OsCl ₃ hydrate, CoCl ₂ , Co ₂ CO ₈ , FeCl ₂ and FeBrl ₂ .

Instead of Deprotonation by addition of a base may also include suitable metal complexes with basic anions, for example the diacetates of Pd (II) or Ni (II) or Rh (I) or Ir (I) compounds which Wear alkoxyligands.

The obtained metal complexes of the formulas IIa, IIb, IIc or IId, as well as the metal complexes of the formulas IIe, IIf or IIg, according to the Expert known methods worked up. The workup can for example by removal of the solvent and subsequent chromatography the product obtained or recrystallization of the product obtained carried out become.

The Imidazolium or imidazolidinium salts of the formulas Ia and Ib, respectively in a molar ratio to the basic anions of generally 2 to 1 to 1 to 2, preferred 1 to 1.2 to 1.2 to 1 used.

at the preparation of metal complexes of the formulas IIa, IIb, IIc or IId are the imidazolium or imidazolidinium salts of the formula Ia or Ib in a molar ratio to the suitable metal complexes of generally 2 to 1 to 1 to 2, preferably 1 to 1.2 to 1.2 to 1 used. Become metal complexes of the formulas IIe, IIf or IIg, the imidazolium or imidazolidinium salts of the formula Ia or Ib in a molar relationship to the suitable metal complexes of generally 4 to 1 to 1.8 to 1, preferably 2.5 to 1 to 2 to 1 used.

The Metal complexes of the invention of the formulas IIa, IIb, IIc or IId, and the formulas IIe, IIf or IIg, can selected in a procedure from the group consisting of hydrogenation, oxidation, hydroformylation, Heck reaction, hydrodimerization, telomerization, comfort Tsuji coupling, Suzuki Clutch, Kumada Clutch, Negishi Clutch, Silent Clutch, Sonogashira reaction, carbonylation, isomerization, rearrangement, Diels-Alder reaction, metathesis reaction, 1,4-functionalization of 1,3-dienes, hydrocyanation, hydrosilylation, oligomerization and polymerization are used. They are generally considered Catalysts used in the reactions mentioned.

An overview to the mentioned chemical reactions can be found in Applied Homogeneous Catalysis with Organometallic Compounds (B. Cornells, W.A. Hermann, Eds.), 2nd Ed., Wiley-VCH, Weinheim 2002.

In the hydrogenation, unsaturated compounds, for example alkenes, alkynes, aromatic compounds, aldehydes, imines or ketones, by reaction with hydrogen or another reducing agent (for example LiAlH ₄ , NaBH ₄ or iso-propanol) on a suitable catalyst to the corresponding saturated or hydrogenated less unsaturated compounds. Examples of suitable catalysts are the metal complexes of ruthenium, cobalt, rhodium, iridium, palladium, nickel and platinum according to the invention. The hydrogenation is generally carried out at a temperature of 0 to 200 ° C and a pressure of atmospheric pressure to 70 MPa abs.

In the oxidation, oxidizable compounds, such as alkanes, olefins, alkynes, alcohols, aldehydes on a suitable catalyst with oxygen or peroxides to epoxides, alcohols, carboxylic acids, carboxylic anhydrides, aldehydes, ketones, phenols, carbon monoxide or carbon dioxide with oxygen, an oxygen-containing Gas mixture or an oxygen carrier such as H ₂ O ₂ , peroxides, inter alia. Examples of suitable catalysts are the metal complexes of vanadium, chromium, molybdenum, tungsten and manganese according to the invention. The oxidation is generally carried out at a temperature of 0 to 200 ° C and a pressure of atmospheric pressure to 70 mPa abs.

at In the hydroforming, olefins are added to a suitable catalyst with water and carbon monoxide to aldehydes or, in combination with a hydrogenation as so-called Eintropfreaktion, to alcohols implemented. Examples of suitable catalysts are the metal complexes according to the invention of cobalt, rhodium, platinum, palladium, ruthenium and platinum / tin called. The hydroformulation is generally carried out at one Temperature from 0 to 200 ° C and a pressure of atmospheric pressure up to 70 MPa abs.

at the Heck reaction are aryl halides, phenols, anilines, benzoic anhydrides, benzoic acid chlorides or vicinal halogenolefins with olefins on a suitable catalyst converted to styrene derivatives or conjugated olefins: as appropriate Catalysts are the metal complexes of the invention with palladium called. The Heck reaction generally occurs at a temperature from 0 to 200 ° C and a pressure of atmospheric pressure up to 32.5 MPa abs. Advantageously, basic compounds such as triethylamine, cesium carbonate or sodium bicarbonate and optionally salt additives such as tetrabutylammonium bromide, Lithium iodide, sodium bromide and the like a. added.

at Hydrodimerisierung be conjugated dienes, for example 1,3-butadiene, in the presence of a suitable catalyst and a Hydride donors such as formates dimerized to dienes. So, for example be obtained from 1,3-butadiene 1,7- and 2,7-octadiene. As appropriate Catalysts are exemplified by the metal complexes of the invention called the palladium. Hydrodimerization generally occurs at a temperature of 20 to 200 ° C and a pressure of atmospheric pressure up to 20 MPa abs. If appropriate, it is advantageous under carbon dioxide pressure to work.

at telomerization becomes conjugated dienes, for example 1,3-butadiene, by reaction at a Brönstedt acid on a suitable catalyst to the corresponding functionalized Serve dimerized. So get For example, from 1,3-butadiene 1,7- and 2,7-Octadienylderivate. As Brönstedt acids are For example, water, alcohols or amines suitable. As appropriate Catalysts are exemplified by the metal complexes of the invention called the palladium. The telomerization generally takes place at a temperature of 20 to 200 ° C and a pressure of atmospheric pressure up to 20 MPa abs. If necessary, it is advantageous in the presence a base such as an alkali hydroxide or a tertiary amine as well as to work under carbon dioxide pressure.

at the consolation Tsuji coupling allyl alcohols, allyl halides or Allyl carboxylates on a suitable catalyst with a compound, which contains an acidic, removable hydrogen atom, such as an amine, a malonic acid derivative or a 1,3-diketone, with substitution of the alcohol, halide or Carboxylatrests implemented. As suitable catalysts exemplified the metal complexes of the invention called the palladium. If necessary, it is advantageous in the presence to work a base. The consolation Tsuji coupling generally occurs at a temperature of 20 to 200 ° C and a pressure of atmospheric pressure up to 20 MPa abs.

at the Suzuki coupling be aryl or alkylboronic or esters with aryl halides, arylphenol esters, anilines, diazonium salts or arylcarboxylic acid derivatives, such as esters, anhydrides or acid chlorides, in the presence of a suitable catalyst to unsymmetrical or implemented symmetrical biaryls. As suitable catalysts exemplified the metal complexes of the invention called palladium or nickel.

Advantageous are solvents such as toluene, dioxane or tetrahydrofuran. Furthermore, it is advantageous to Activation of the catalyst to supply fluoride or a base. The Suzuki coupling generally occurs at a temperature of 20 to 200 ° C and a pressure of atmospheric pressure up to 20 MPa abs. The Suzuki coupling is described, for example, in J. Hassan Chem. Rev. 102, 2002, pages 1359-1469.

at The Kumada coupling becomes aryl or alkyl magnesium halides (Grignard compounds) and in the Negishi coupling, aryl or alkyl zinc halides with aryl halides, Arylphenolestern, anilines or diazonium salts in the presence of a suitable catalyst to unsymmetrical or symmetrical biaryls implemented. Examples of suitable catalysts are the metal complexes of the invention Palladium or nickel, called. Advantageous solvents are, for example Toluene, dioxane or tetrahydrofuran. The Kumada clutch and the Negishi coupling generally occurs at a temperature of 20 to 200 ° C and a pressure of atmospheric pressure up to 20 MPa abs. The Kumada clutch and the Negishi clutch are For example, in J. Hassan et al., Chem. Rev. 102, 2002, p 1359 to 1469 described.

at the Stille coupling become aryl or alkylstannanes with aryl halides, Arylphenol esters, anilines, diazonium salts or arylcarboxylic acid derivatives, such as esters, anhydrides or acid chlorides, in the presence of a suitable catalyst to unsymmetrical or implemented symmetrical biaryls. As suitable catalysts exemplified the metal complexes of the invention called palladium or nickel. Advantageous are solvents such as toluene, dioxane, tetrahydrofuran or dimethylformamide. Furthermore it is advantageous for activating the catalyst, a copper-containing To supply compound such as Cul or CuO. The silence clutch takes place generally at a temperature of 20 to 200 ° C and a Pressure of atmospheric pressure up to 20 MPa abs. The Stille coupling is for example in J. Hassan Chem. Rev. 102, 2002, pages 1359-1469.

at the Sonogashira reaction involves terminal alkynes with aryl halides, Arylphenol esters, anilines, diazonium salts, vicinal halogenolefins or arylcarboxylic acid derivatives, such as esters, anhydrides or acid chlorides, in the presence of a suitable catalyst to substituted alkynes implemented. Examples of suitable catalysts are the metal complexes according to the invention of palladium, nickel or copper. Solvents such as toluene, dioxane or tetrahydrofuran or amines are advantageous. Furthermore it is advantageous to activate the catalyst, a copper-containing To supply compound like Cul. Further It may be advantageous to use a base such as triethylamine or Add diethylamine. The Sonogashira reaction generally occurs at a temperature of 20 to 200 ° C and a pressure of atmospheric pressure up to 20 MPa abs. The Sonogashira reaction is described, for example, in J. Hassan et al., Chem. Rev. 102, 2002, pages 1359-1469.

In the carbonylation olefins, alcohols, ethers, esters or halogen compounds in counter wart of a suitable catalyst with carbon monoxide and a nucleophilic compound such as water, alcohols or amines converted to the corresponding carboxylic acid derivatives. Examples of suitable catalysts are the metal complexes of palladium, nickel, cobalt, iridium or rhodium according to the invention. The carbonylation is generally carried out at a temperature of 0 to 200 ° C and a pressure of atmospheric pressure to 32.5 MPa abs.

at the metathesis reaction, two olefins in the presence of a suitable Catalyst reacted to form two olefins. As appropriate Catalysts are exemplified by the metal complexes of the invention of ruthenium, osmium, rhenium, molybdenum, tungsten or titanium. Be as additions optional z. As tetramethyltin, alkylaluminum chlorides, copper (I) chloride or pyridines added. The metathesis reaction is for example in K.J. Ivin et al., Olefin Metathesis and Metathesis Polymerization, Academic Press, 1997, and R.H. Grubbs (Ed.), Handbook of Metathesis, Wiley-VCH, 2003 described.

at the hydrocyanation become olefins in the presence of suitable catalysts reacted with hydrogen cyanide to form cyanoalkanes. As suitable catalysts Examples are the metal complexes of nickel according to the invention called.

at hydrosilylation are unsaturated compounds such as alkenes, Alkynes, aldehydes, imines or ketones, by reaction with an organic or inorganic silicone hydride on a suitable catalyst to the corresponding saturated or less unsaturated Implemented organosilicon compounds. Suitable catalysts the metal complexes of the invention.

at Arylaminierung be aryl halides in the presence of suitable catalysts reacted with amines. As suitable catalysts are exemplary the metal complexes of the invention called the palladium.

The Metal complexes of the invention of the formulas IIa, IIb, IIc or IId, as well as the metal complexes according to the invention of formulas IIe, IIf and IIg in combination with metal addition as catalysts for Lewis acid catalyzed Reactions are used.

at the isomerization are carried out in the presence of a suitable catalyst Double bonds shifted within a carbon skeleton. As appropriate Catalysts are exemplified by the metal complexes of the invention of ruthenium, rhodium, copper or scandium and other Lewis acids.

Under Stock transfers are, for example, the Cope rearrangement and the Beckmann rearrangement. They are generally made by Lewis acids, for example by Catalyzes scandium or titanium compounds. Suitable scandium or titanium compounds are the metal complexes of the invention of scandium or titan.

at The Diels-Alder reaction becomes a diene in the presence of a suitable Catalyst with a dienophile, for example an olefin, a Alkyne or a carbonyl, reacted to form a six-membered ring. Suitable catalysts are generally Lewis acids, for example Copper, scandium or titanium compounds, used. Suitable copper, scandium or titanium compounds are the metal complexes of the invention of copper, scandium or titanium.

Further Lewissäurekatalysierte Reactions in which the metal complexes of the invention are used can be are z. In J. March, Advanced Organic Chemistry, John Wiley & Sons, 1985.

Of Further can the metal complexes of the invention also be catalytically active without added metal, if they are as Lewis bases be used. So can for example for the oligomerization and polymerization of epoxides, lactones or Lactams or the copolymerization of epoxides and CO used become. Other Lewis base catalyzed reactions are, for example in J. March, Advanced Organic Chemistry, John Wiley & Sons, 1985.

at the polymerization, monomers in the presence of a suitable Catalyst converted to polymeric compounds. As monomers may be exemplified linear olefins, cyclic olefins, acrylates, methacrylates, vinyl ethers, Butadiene, acrylonitrile, epoxides, carbon monoxide, oxygen, lactams, Lactones or alkynes can be used.

It can Homopolymers or by using more than one monomer copolymers getting produced. The polymerization is for example in G. Odian, Principles of Polymerization, Wiley & Sons 1991.

at The oligomerization of monomers in the presence of a suitable Catalyst to the corresponding higher molecular weight compounds oligomerized. If dimers are formed, one speaks of one Dimerization, trimers are formed, it is called one Trimerization.

When suitable catalysts for the polymerization and oligomerization are exemplary of the metal complexes of the invention of nickel, palladium, iron, cobalt, titanium, zirconium, hafnium, aluminum, Copper, manganese, ruthenium, osmium, tungsten, molybdenum, titanium or rhenium.

For the polymerization of olefins, for example, the metal complexes of Nickel, palladium, iron, cobalt, chromium, titanium, hafnium and zirconium used. To activate the compounds activators such. B. Aluminum alkyl compounds or boron compounds are added.

For the copolymerization of CO and olefins, for example, the metal complexes of the invention used of nickel or palladium. As activators acids can be added become.

For the copolymerization Olefins and acrylates, for example, the metal complexes of the invention used of nickel or palladium. As activators z. As aluminum alkyl compounds or boron compounds are added.

radically polymerizable monomers can in an atom transfer radical polymerization (ATRP) are converted to polymers. These are preferably copper, Iron or ruthenium derivatives of the metal complexes of the invention used.

The The above-mentioned chemical reactions may be batchwise, semi-continuous or carried out continuously become.

The The above-mentioned methods can in the liquid phase carried out be, by reacting the starting materials in the presence of at least one the metal complexes of the invention with a high conversion, a high selectivity, a high yield and a high space-time yield.

The The above-mentioned chemical reactions can be carried out in different solvents. If a polymerization is carried out in water, dispersions can be obtained become. It can For this purpose, additional auxiliaries such as emulsifiers are added.

The aforementioned catalytic reactions may also be carried out in an asymmetric form, for example when the compounds of the invention contain an asymmetric center. This is possible, for example, when: one or more substituents R ¹ to R ⁹ or R ¹ 'to R ⁹ ' are themselves asymmetric, or at least one pair of these substituents bonded to a single carbon atom of the ligand backbone, for example the substituents R ³ and R ⁴ are different.

The Metal complexes of the invention of the formulas IIa, IIb, IIc and IId as well as IIe, IIf and IIg, or the compounds of formulas Ia or Ib together with a carrier material be used. For example, you can the metal complexes or Verbindun conditions linked to the carrier material or by interaction of the polar metal complex with the polar one support material be connected.

When support material Both inorganic and organic compounds are suitable.

preferred inorganic compounds are porous oxides, inorganic chlorides, Clay, clay minerals and layer compounds.

Suitable porous oxides include SiO ₂ (preferably monolithic SiO ₂ ), Al ₂ O ₃ , MgO, ZrO ₂ , TO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _2, and mixtures of compounds containing these oxides, such as natural or synthetic zeolites, mixed oxides such as SiO ₂ -MgO, SiO ₂ -Al ₂ O ₃ , SiO ₂ -TeO ₂ , SiO ₂ -V ₂ O ₅ , SiO ₂ -Cr ₂ O ₃ and SiO ₂ -TiO ₂ -MgO or MOFs (Metal Organic Frameworks, M. Yagi et al., Angew Chem .. Int Ed 2002, 41, No. 2, 284-287 or Angew Chem Chem Int Ed 1999, 38, No. 17, 2590 - 2594). SiO ₂ (be preferably on monolithic SiO ₂ ), Al ₂ O ₃ , TiO ₂ , ZrO ₂ , mixed oxides such as SiO ₂ / Al ₂ O ₃ and MOFs.

The inorganic oxides can Furthermore, small amounts of carbonates, sulfates, nitrates or Contain oxides.

The porous oxides used according to the present invention preferably have a particle diameter of 10 to 300 μm, more preferably 20 to 200 μm and a specific surface area of generally 50 to 1000 m ² / g, preferably 100 to 700 m ² / g and a pore volume of generally 0.3 to 3 cm ³ / g. The support material may be calcined before use at generally 100 to 1000 ° C, preferably 150 to 700 ° C, if necessary.

suitable inorganic oxides, clay, clay minerals and layered compounds for example, in EP-A 0 950 667.

suitable organic carrier materials are grainy, for example or particulate solid compounds with a particle diameter of generally 10 to 300 μm. examples for such compounds include (co) polymers formed by reacting an alpha-olefin with 2 to 14 carbon atoms such as ethylene, propylene, 1-butene or 4-methyl-1-pentene were prepared as main monomers, (co) polymers by reaction of vinylcyclohexane or styrene as major monomers and derivatives of said (co) polymers are preferred polymers functionalized polystyrenes.

The explain the following examples the invention additionally:

Examples

2-imidazol-1-yl-2-methyl-1-phenylpropane-1-one

To a solution of 3.40 g of imidazole (49.9 mmol) in 40 ml of ethanol is added 4 ml of 2-bromoisobutyrophene (23.8 mmol). The resulting mixture is refluxed for 3 days. A quantitative conversion can not be achieved, thin-layer chromatography reaction control shows traces of starting material. The solution is mixed with water and methylene chloride, the organic phase washed 3x with water and 2x with saturated NaCl solution, and dried over Na ₂ SO ₄ . The CH ₂ Cl ₂ is stripped off on a rotary evaporator and the pale yellow oil is crystallized at -30 ° C. The white solid is recrystallized from CH ₂ Cl ₂ / hexane.
Yield: 3.11 g (61%), empirical formula: C ₁₃ H ₁₄ N ₂ O, color: white
¹ H-NMR (DMSO-d ₆ ): 1.80 (s, 6H, -CH ₃ ); 6.94-7.87 (m, 8H, aromatic protons)

N - [[2- (imidazol-1-yl)] - 2-methyl-1-phenyl-1-propylidenphenyl] amine

524 μl of aniline (5.75 mmol) are dissolved in 40 ml of toluene and 2.87 ml of Al (CH ₃ ) ₃ (5.75 mmol), 2M in toluene are added. The solution is heated to 80 ° C, after about 30 min starts gas evolution (CH ₄ ), which is complete after 90 min. The solution cooled to room temperature is added with the white 2-imidazol-1-yl-2-methyl-1-phenylpropan-1-one (560 mg, 2.61 mmol). The reaction mixture is first at room temperature overnight, then stirred at 80 ° C for 3 h. The result is a yellow, clear solution. This is cooled to 0 ° C and carefully quenched with ice. After addition of methylene chloride, the organic phase is washed 3x with 5% NaOH, then 2x with water, dried over Na ₂ SO ₄ and concentrated by rotary evaporation. By chromatography with Et ₂ O / hexane = ½ as the eluent excess aniline is removed, the condensation product can be eluted with MeOH in very good purity.
Yield: 651 mg (86%), empirical formula: C ₁₉ H ₁₉ N ₃ , color: yellow oil
¹ H-NMR (CD ₂ CL ₂ ): 1.85 (s, 6H, -CH ₃ ); 6.39-7.53 (m, 13H, aromatic protons)
MS (FAB pos): (M + H ⁺ ) = 290.2 m / z

N - [[2- (imidazol-1-yl)] - 2-methyl-1-phenyl-1-propylidene-2,6-diisopropyl-phenyl] amine

2.96 ml of 2,6-diisopropylaniline (15.7 mmol) are dissolved in 40 ml of toluene and treated with 7.84 ml of Al (CH ₃ ) ₃ (15.7 mmol, 2M in toluene). The solution is heated to 80 ° C, after about 30 min starts gas evolution (CH ₄ ), which is complete after 120 min. The solution cooled to room temperature is added with the white 2-imidazol-1-yl-2-methyl-1-phenylpropan-1-one (1.12 g, 5.23 mmol). The reaction mixture is warmed to 80 ° C and stirred for 48 h. The result is an intense yellow, clear solution. This is cooled to 0 ° C and carefully quenched with ice. After addition of methylene chloride, the organic phase is washed 3x with 5% NaOH, then 2x with water, dried over Na ₂ SO ₄ and concentrated by rotary evaporation. By chromatography with Et ₂ O / hexane = 1/1 as the eluent excess 2,6-diisopropylaniline is removed, the condensation product can be eluted with MeOH in very good purity.
Yield: 1.46 g (75%), empirical formula: C ₂₅ H ₃₁ N ₃ , color: yellow oil
¹ H-NMR (CD ₂ CL ₂ ): 1.05-1.07 (d, 6H, -CH ₃ isopropyl); ³ J _{H, H} : 6.94 Hz; 1:13 to 1:15 (d, 6H, CH ₃ isopropyl) ³ J _{H, H:} 6.61 Hz; 1.90 (s, 6H, -CH3); 2.74 (m, 2H, -CH); 6.38-7.49 (m, 11H, aromatic protons)
MS (El pos): M ⁺ = 373.3 m / z

1- [2'-methyl-1'-phenyl-1'-1'phenylimino-propylidene] -3-methylimidazoliumtriflat

650 mg of N - [[2- (imidazol-1-yl)] - 2-methyl-1-phenyl-1-propylidenephenyl] amine (2.25 mol) are dissolved in 40 ml of CH ₂ Cl ₂ and cooled to -80 ° C , The yellow, clear solution is injected with 246 μl of methyl triflate (2.25 mmol), then it is stirred at -80 ° C. for 90 min. The cold bath is then removed and stirring is continued for a further 90 minutes at room temperature. The methylene chloride is then stripped off in a high vacuum and the pale yellow residue is washed twice with diethyl ether and dried to constant weight.
Yield: 920 mg (90%), empirical formula C ₂₁ H ₂₂ F ₃ N ₃ O ₃ S, color: yellow
¹ H-NMR (DMSO-d ₆ ): 1.36 (s, 6H, -CH ₃ ); 3.33 (s, 3H, -NCH ₃ ); 6.03-7.54 (m, 12H, aromatic protons); 8.84 (s, 1H, N-CH = N)
MS (FAB pos): M ⁺ = 304.1 m / z (cation)

1- [2'-methyl-1'-phenyl-1 '- [2,6-diisopropylphenylimino] -1'-propylidene] -3-methyl-imidazolium triflate

1.47 g of N - [[2- (imidazol-1-yl)] - 2-methyl-1-phenyl-1-propylidene-2,6-diisopropyl-phenyl] -amine (3.94 mmol) are dissolved in 40 ml of CH ₂ Cl ₂ dissolved and cooled to - 80 ° C. The yellow, clear solution is injected with 432 μl of methyl triflate (3.94 mmol), then it is stirred at -80 ° C. for 90 min. The cold bath is then removed and stirring is continued for a further 90 minutes at room temperature. The methylene chloride is then stripped off under high vacuum and the pale yellow residue is washed twice with diethyl ether and dried to constant weight.
Yield: 2.00 g (95%), empirical formula: C ₂₇ H ₃₄ F ₃ N ₃ O ₃ S, color: bright yellow
¹ N-NMR (DMSO-d ₆ ): 0.90-0.92 (d, 6H, -CH ₃ isopropyl) ³ J _{H , H} : 6.61 Hz; 1:04 to 1:07 (d, 6H, CH ₃ isopropyl) ³ J _{H, H:} 6.932.00 (s, 6H, -CH _3); 2.65 (m, 2H, -CH isopropyl); 3.87 (s, 3H, -NCH ₃ ); 6.82-8.10 (m, 10H, aromatic protons); 8.94 (s, 1H, N-CH = N)
MS (FAB pos): M ⁺ = 388.4 m / z (cation)

1- [2'-methyl-1'-phenyl-1'-iminophenylpropyliden] -3-methylimidazolidin-2-ylidene wolframtetracarbonyl

180 mg of 1- [2'-methyl-1'-phenyl-1'-phenylimino-1'-phenylimino-1'-propylidene] -3-methylimidazolium triflate (0.397 mmol) were dissolved in 30 ml of THF and 16 mg KH (0.397 mmol) was added. After deprotonation (about 1 h, no more gas evolution detectable) were added 140 mg of W (CO) 6 (0.397 mmol). The tungsten hexacarbonyl does not dissolve completely, the slightly cloudy solution is then irradiated for 2 × 90 minutes with a photolamp. By means of TLC, a quantitative conversion can be determined, since the very apolar W (CO) _{6 has} completely disappeared. The solvent is removed and the brown residue is chromatographed (column length: 6 cm, diameter: 3 cm, Et ₂ O / hexane = 1/1 as eluent). The yellow, crystalline solid is dried under high vacuum to constant weight.
Yield; 60 mg (25%), molecular formula: C ₂₄ H ₂₁ N ₃ O ₄ W, color: yellow
IR (cm ^-1 ): 3206 (w), 3057 (w), 1990 (vs), 1865 (vs), 1819 (vs), 1576 (m), 1466 (m), 1440 (s), 1390 (m ), 1360 (s), 1287 (m), 1216 (s), 1125 (m), 1077 (m), 990 (m), 719 (s), 704 (s), 694 (s), 683 (s )

Catalytic use of 1- [2'-methyl-1'-phenyl-1'-iminophenylpropylidene] -3-methylimidazolin-2-ylidene in palladium-catalyzed Suzuki reaction

1- [2'-Methyl-1'-phenyl-1'-phenylimino-1'-propylidene] -3-methyl-imidazolium triflate (0.4 mmol) are dissolved in 30 ml dioxane and treated with 16 mg KH (0.4 mmol). After deprotonation (about 1 h, no gas evolution detectable) 0.4 mmol Pd (OAc) _{2 are} added. After stirring for 1 hour, 2.0 mmol of 4-bromotoluene, 2.0 mmol of phenylboronic acid and 4 mmol of CsCO _{3 are} added. After 48 hours at 80 ° C 4-methyldiphenyl is obtained with almost complete conversion.

Claims (11)

Compounds of the general formulas Ia or Ib

wherein: in formula Ia: EN, As, P; R ^{1 is} hydrogen, a linear, branched or cyclic alkyl radical, an unsubstituted or substituted aryl radical; R ^{2 is} hydrogen, a linear, branched or cyclic alkyl radical, an unsubstituted or substituted aryl radical; R ³ , R ⁴ independently of one another are a linear, branched or cyclic alkyl radical, an unsubstituted or substituted aryl radical; R ^{5 is} hydrogen, a linear, branched or cyclic alkyl radical, an unsubstituted aryl radical or a radical of the formula

wherein R ¹ ', R ² ', R ³ 'and R ⁴ ' have the meanings given for R ¹ , R ² , R ³ and R ⁴ ; R ⁶ , R ⁷ are each independently hydrogen, a linear, branched or cyclic alkyl radical, an unsubstituted or substituted aryl radical, halogen or a nitro group or R ⁶ and R ⁷ together with the carbon atoms to which they are attached form a 4-10 -membered ring which may be saturated or unsaturated and may optionally have one or two heteroatoms; X ^- an anionic radical; and in formula Ib: E, E ', R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ¹ ', R ² ', R ³ ', R ⁴ ', R ⁶ , R ⁷ and X ^- the meanings given with respect to formula Ia, and R ⁸ , R ⁹ independently of one another are hydrogen, a linear, branched or cyclic alkyl radical, an unsubstituted or substituted aryl radical, halogen or a nitro group. Compounds according to claim 1, characterized that E and optionally E 'N mean. Compounds according to claim 1 or 2, characterized in that R ³ and R ^{4 are} linear or branched alkyl radicals having 2 to 10 carbon atoms, phenyl, tolyl or cumyl. Compounds according to one of claims 1 to 3, characterized in that R ^{5 represents} a linear or branched alkyl radical having 1 to 10 carbon atoms or phenyl, naphthyl, tolyl or cumyl. Process for the preparation of compounds (imidazolium salts) of the formula Ia comprising the following steps: i) reaction of imidazole or a derivative thereof with a carbonyl compound of the formula VII to give a carbonyl compound of the formula IIIa

Hal = halogen, preferably Cl or Br; ii) subsequent reaction of the carbonyl compound of the formula IIIa with a compound of the formula IV, preferably an amine, forming a compound of the formula Va

iii) reaction of the compound of the formula Va with a salt of the formula VI to give the desired compound of the formula Ia

wherein EN, As, P; R ^{1 is} hydrogen, a linear, branched or cyclic alkyl radical, an unsubstituted or substituted aryl radical; R ^{2 is} hydrogen, a linear, branched or cyclic alkyl radical, an unsubstituted or substituted aryl radical; R ³ , R ⁴ independently of one another are a linear, branched or cyclic alkyl radical, an unsubstituted or substituted aryl radical; R ^{5 is} hydrogen, a linear, branched or cyclic alkyl radical, an unsubstituted aryl radical or a radical of the formula

wherein R ¹ ', R ² ', R ³ 'and R ⁴ ' have the meanings given for R ¹ , R ² , R ³ and R ⁴ ; R ⁶ , R ⁷ are each independently hydrogen, a linear, branched or cyclic alkyl radical, an unsubstituted or substituted aryl radical, halogen or a nitro group or R ⁶ and R ⁷ together with the carbon atoms to which they are attached form a 4-10 -membered ring which may be saturated or unsaturated and may optionally have one or two heteroatoms; X ^- an anionic radical; Use of compounds of the formulas Ia or Ib according to one of claims 1 to 4 as precursors for functionalized carbene ligands for the preparation of metal complexes. Metal complexes of the general formulas IIa, IIb, IIc, IId, IIe, IIf or IIg

in which mean: in formulas IIa, IIc, IIe or IIg EN, As, P; R ^{1 is} hydrogen, a linear, branched or cyclic alkyl radical, an unsubstituted or substituted aryl radical; R ^{2 is} hydrogen, a linear, branched or cyclic alkyl radical, an unsubstituted or substituted aryl radical; R ³ , R ⁴ independently of one another are a linear, branched or cyclic alkyl radical, an unsubstituted or substituted aryl radical; R ^{5 is} hydrogen, a linear, branched or cyclic alkyl radical, an unsubstituted or substituted aryl radical; R ⁶ , R ⁷ independently of one another represent hydrogen, a linear, branched or cyclic alkyl radical, a substituted or unsubstituted aryl radical, halogen or a nitro group, or R ⁶ and R ⁷ together with the carbon atoms to which they are attached have a 4- to 10- membered saturated or unsaturated ring, optionally one or two heteroatoms may form; R ^{1 '',} R ^{2 ',} R ^3' and R ^{4 ''} have the R ^'for R ^1, R ^2, R ^3, and ⁴ defined above; E '' has the meanings given for E; M metal atom of Group 3 to 13 of the Periodic Table of the Elements; Y monoanionic ligand may be mono- or bidentate; L neutral mono- or bidentate ligand; n number of ligands Y from 0 to 6, wherein the ligands Y may be the same or different at n greater than 1; m number of ligands L from 0 to 6, wherein the ligands L may be the same or different at m greater than 1; where n is chosen such that the charge of all ligands Y corresponds to the valency of the metal atom used, and the sum of n and m depends on the coordination number of the metal atom used and the denticity of the ligands Y and L and the number and denticity of the functionalized carbene ligand used is; and in the formulas Ib, Id, If and Ig denote E, E ', E ", R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ¹ ', R ² ', R ³ ', R ⁴ ', R ^{1 "} , R ^2" , R ^{3 "} , R ⁴ ", R ^{5 '} , R ^6' , R ^{7 '} , M, Y, L, n and m are the with respect to the formulas Ia and Ic, and R ⁸ , R ⁹ , R ^{8 '} , R ^9' independently of one another are hydrogen, a linear, branched or cyclic alkyl radical, an unsubstituted or substituted aryl radical, halogen or a nitro group. Metal complex according to Claim 7, characterized that the metal atom M is selected is selected from the group consisting of Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Ti, Zr, V, Mn, Sc, Cr, Mo, W, Fe, Cu, Ag and Al, preferably Ni, Pd, Ru, Os, Co, Rh, Ir, Pt, Ti, Zr, V, Mn, Fe and Sc. Metal complex according to claim 7 or 8, characterized the monoanionic ligand Y, which may be mono- or bidentate, selected is selected from the group consisting of halides, pseudohalides, Cyclopentadienyl, the cyclopentadienyl groups having alkyl substituents, preferably methyl or tert-butyl, may be substituted, especially preferably with five Methyl groups, so that the substituted cyclopentadienyl Pentamethylcyclopentadienyl indenyl, where the indenyl radical is optionally substituted with alkyl substituents, preferably methyl, may be substituted, alkyl radicals, with the Metal atom M over a σ bond connected are alkylaryl radicals which are linked to the metal atom M via a σ bond, Alcoholates, trifluorosulfonates, carbenes, acetylacetonate and its Derivatives, carboxylates, amino acid groups, Picolinsäuregruppen and its derivatives. Process for the preparation of a metal complex according to one the claims 7 to 9 by deprotonation of the corresponding compound of the formula Ia or Ib according to one the claims 1 to 4 and subsequent Implementation with a metal complex. Use of metal complexes according to any one of claims 7 to 9 in a process selected from the group consisting of hydrogenation, oxidation, hydroformylation, Heck reaction, hydrodimerization, telomerization, comfort Tsuji coupling, Suzuki coupling, Kumada coupling, Negishi coupling , Stille Coupling, Sonogashira Reaction, Carbonylation, Isomerization, Rearrangement, Diels-Alder Reaction, Metathesis Reaction, 1,4-Functionalization of 1,3-Dienes, Hydrocyanation, Hydrosilylation, Oligomerization and polymerization.