Transition metal complexes with diaminocarbene ligands and their use in reactions catalyzed by transition metals
View Patent ↗The invention relates to novel transition metal complexes containing at least one diaminocarbene ligand, to processes for preparing these transition metal complexes and to their use as catalysts in organic reactions.
1. Compound of the general structural formula (I),
where
M is transition metal of transition groups 6 to 8 of the Periodic Table,
R 1 , R 2 , R 3 and R 4 are identical or different and are hydrogen and/or hydrocarbon groups, where the hydrocarbon groups are identical or different, straight-chain, branched or cyclic radicals selected from the group consisting of alkyl radicals having from 1 to 50 carbon atoms, alkenyl radicals having from 2 to 50 carbon atoms, alkynyl radicals having from 2 to 50 carbon atoms and aryl radicals having from 6 to 30 carbon atoms in which at least one hydrogen atom is replaceable by a functional group, and/or
R 1 and R 2 and/or R 3 and R 4 are part of a cyclic system which is identical or different, where the cyclic system comprises a carbon framework having from 2 to 20 carbon atoms and a nitrogen atom in formula (I), where the carbon atoms of R 1 and R 2 and/or R 3 and R 4 in formula (I) are not counted and where at least one hydrogen atom in the ring is replaceable by a functional group and/or at least one carbon atom of the ring is replaceable by a heteroatom selected from the group consisting of S, P, O and N, and/or
R 1 and/or R 2 and/or R 3 and/or R 4 are linked to one of the ligands L via a bridge having from 1 to 20 carbon atoms, where the carbon atoms of R 1 , R 2 R 3 and R 4 are not counted, and
L is an identical or independently different uncharged two-electron donors and/or is a part of a cyclic system and/or is anionic ligands, and
n is an integer.
2. Compounds according to claim 1 , wherein L is an identical or independently different uncharged two-electron donor selected from the group consisting of amines, imines, phosphines, phosphites, stibines, arsines, CO, carbonyl compounds, nitriles, alcohols, thiols, ethers, thioethers and pyridines, and/or
identical or independently different uncharged two-electron donor selected from the group consisting of N-heterocyclic carbenes of the general formula (A-E)
where
the radicals R 5 , R 6 , R 7 and R 8 are identical or different and are hydrogen and/or hydrocarbon groups, where the hydrocarbon groups are identical or different, straight-chain, branched or cyclic radicals selected from the group consisting of alkyl radicals having from 1 to 50 carbon atoms, alkenyl radicals having from 2 to 50 carbon atoms, alkynyl radicals having from 2 to 50 carbon atoms and aryl radicals having from 6 to 30 carbon atoms in which at least one hydrogen atom is replaceable by a functional group, and/or
the radicals R 6 and R 7 are identical or independently different halogen, nitro, nitroso, alkoxy, aryloxy, amido, carboxyl, carbonyl, thio or/and sulfonyl groups, and/or
identical or independently different uncharged two-electron donors selected from the group consisting of diaminocarbene ligands of the general formula (II),
where
the radicals R 1 , R 2 , R 3 and R 4 are as defined in claim 1 , and/or identical or independently different uncharged two-electron donor ligands selected from the group consisting of compounds of the general formulae (III) and (IV)
where
the radicals R 9 and R 10 are identical or different and are hydrogen or/and hydrocarbon groups, where the hydrocarbon groups are identical or different, straight-chain, branched or cyclic radicals selected from the group consisting of alkyl radicals having from 1 to 50 carbon atoms, alkenyl radicals having from 2 to 50 carbon atoms, alkynyl radicals having from 2 to 50 carbon atoms, aryl radicals having from 6 to 30 carbon atoms and silyl radicals in which at least one hydrogen atom is replaceable by an alkyl, aryl, alkenyl, alkynyl, metallocenyl, halogen, nitro, nitroso, hydroxy, alkoxy, aryloxy, amino, amido, carboxyl, carbonyl, thio or/and sulfonyl group.
3. The compound according to claim 1 , wherein L is an identical or independently different anionic ligand selected from the group consisting of halides, pseudohalides, hydroxides, alkoxides, thiolates, carboxylates and sulfonates.
4. The compound according to claim 3 wherein the pseudohalides are selected from the group consisting of cyanide, thiocyanate, cyanate, isocyanate and isothiocyanate.
5. The compounds according to claim 1 , wherein L is a cyclic diene.
6. The compound according to claim 1 , wherein M is rhodium or iridium and n is 3 and L 1 , L 2 and L 3 are identical or/and independently different and/or are part of a cyclic system, where
L 1 is an anionic ligand selected from the group consisting of halide, alkoxide, carboxyl compound, thiolate and pseudohalide or is an uncharged two-electron donor selected from the group consisting of alkenes, alkynes, phosphines, amines, imines, phosphites, stibines, arsines, CO, carbonyl compounds, nitriles, alcohols, ethers, thiols and thioethers and
L 2 and L 3 are identical or independently different and are uncharged two-electron donors selected from the group consisting of alkenes, alkynes, phosphines, amines, imines, phosphites, stibines, arsines, CO, carbonyl compounds, nitriles, alcohols, ethers, thiols and thiolethers or, are part of a cyclic diene.
7. The compound of claim 6 wherein L 2 and L 3 are part of a cyclic diene.
8. The compound of claim 6 wherein L 2 and L 3 together represent 1,5-cyclooctadiene.
9. The compound according to claim 1 , wherein M is ruthenium or osmium and n is 4 and
L 1 and L 2 are identical or independently different and are each an anionic ligand selected from the group consisting of halide, alkoxide, carboxyl compound, thiolate and pseudohalide, with preferred pseudohalides being cyanide, thiocyanate, cyanate, isocyanate and isothiocyanate, and
L 3 is a carbene ligand of the general formula (III) or (IV) according to claim 2 and
L 4 is an uncharged two-electron donor selected from the group consisting of amines, imines, phosphines, phosphites, stibines, arsines, CO, carbonyl compounds, nitriles, alcohols, thiols, ethers and thioethers or is an uncharged two-electron donor ligand selected from the group consisting of N-hetrero-cyclic carbenes of the general formulae A-E according to claim 2 or is a diaminocarbene ligand of the general formula (II) according to claim 2 .
10. Process for preparing the compound according to claim 1 comprising
a) preparing a carbene ligand of the formula (II) according to claim 2 by deprotonation of a formamidinium salt with strong bases or by the “ammonium method” and
b) reacting the carbene ligand of the formula (II) with suitable transition metal complexes in a ligand exchange reaction.
11. Process for preparing the compound according to claim 1 comprising reacting compounds of the type [R 1 R 2 N—CH═NR 3 R 4 ] + X − , where R 1 to R 4 are as defined in claim 1 , with transition metal complexes in a salt metathesis.
12. Process for preparing the compound according to claim 1 comprising reacting compounds of the type [R 1 R 2 N—CH═NR 3 R 4 ] + X − , where R 1 to R 4 are as defined in claim 1 , with alkali metal alkoxides and subsequently reacting the alkoxide adduct formed with transition metal complexes in a ligand exchange reaction.
13. A process for catalyzing hydrosilylation with the compound according to claim 1 .