| 摘要 |
The invention relates to ferrocenyldiphosphine ligands containing a silylene group, ferrocenyldiphosphines bound to inorganic or polymeric organic supports by this silylene group, their preparation and also their metal complexes with transition metals such as rhodium or iridium. The invention also relates to the use of these complexes for hydrogenating organic double or triple bonds, in particular olefinic double bonds and carbon-heteroatom double bonds. The complexes are particularly suitable for enantioselective hydrogenation using chiral diphosphines and prochiral unsaturated compounds. The preparation of these immobilized ferrocenyldiphosphines has only been made possible by the provision of correspondingly functionalized ferrocenyldiphosphines. These compounds and their preparation are likewise novel. Accordingly, the invention also provides compounds of the formula I <IMAGE> (I) in which R1 is C1-C8alkyl, phenyl or phenyl substituted by from 1 to 3 C1-C4alkyl or C1-C4alkoxyalkoxy groups; R2, R3, R10 and R11 are, independently of one another, C1-C12alkyl, C5-C12cycloalkyl, phenyl, C5-C12cycloalkyl substituted by C1-C4alkyl or C1-C4alkoxy, or phenyl substituted by from one to three C1-C4alkyl, C1-C4alkoxy, -SiR4R5R6, halogen, -SO3M, -CO2M, -PO3M, -NR7R8, -[+NR7R8R9]X- or C1-C5fluoroalkyl groups; or the groups -PR2R3 and -PR10R11 are each, independently of one another, a radical of the formula II, IIa, IIb or IIc <IMAGE> (II) <IMAGE> (IIa) <IMAGE> (IIb) <IMAGE> (IIc) and R4, R5 and R6 are, independently of one another, C1-C12alkyl or phenyl; R7 and R8 are H, C1-C12alkyl, phenyl or R7 and R8 are together tetramethylene, pentamethylene or 3-oxa-1,5-pentylene, R9 is H or C1-C4alkyl; R12 are identical or different radicals and are, independently of one another, C1-C12alkyl, C3-C7cycloalkyl, benzyl or phenyl or together are C5-C12alkylene and R13 is C1-C12alkylene or phenylene, M is H or an alkali metal, X- is the anion of a monobasic acid, Z is CI, NH2, NH-C1-C12alkyl, or a group -A-CO-NH-R14-Si(Ra)n (OR15)3-n, in which A is NH or N(C1-C12alkyl), R14 is C1-C12alkylene, R15 is C1-C12alkyl, Ra is C1-C4alkyl or OR15, n is 0, 1 or 2; where the compounds of the formula I are present in the form of their racemates and diastereomers or mixtures of diastereomers.
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