RHODIUM(I)-MONO- UND -DIAZADIENEKOMPLEXE, SYNTHESE, SPEKTROSKOPISCHE CHARAKTERISIERUNG, OXIDATIVE ADDITIONSREAKTIONEN UND EINSATZ IN DER HOMOGENEN KATALYSE ZUR HYDROSILYLIERUNG

Article abstract of DOI:10.1016/0022-328X(86)80012-2

The reaction of(Rh(CO)2Cl)2 with di- and monoazadienes gives planar, four-coordinated rhodium(I) complexes Rh(CO)Cl(DAD) (III) and Rh(CO)Cl(MAD)2 (V), respectively, which catalyse the hydrosilylation of alkenes and alkynes.In a stereoselektive cis-addition symmetric internal alkynes give the corresponding silyl alkenes, while the catalytic addition of silane to terminal alkynes leads to the 2-silyl and cis-and trans-1-silyl-alkenes; their ratio depends on the controlling ligand and on the reaction conditions.With a stoichiometric amount of the silane the complexes III react under oxidative addition to give the rhodium(III) complexes Rh(H)(SiR3)(DAD)Cl (VI), which also catalyse the hydrosilylation.