Organosilicon chemistry. Part 23. Some silylcobalt(III) complexes and the homogeneous catalysis of deuteriation, hydrosilylation, and O-silylation reactions

The complexes [CoH(X2)L3](X = H or N; L = PPh3) react with silanes, SiR3H, to give the new silylcobalt(III) complexes [CoH2(SiR3)L3][R3= F3, MeF2, or (OEt)3]. The characterization of these complexes and their reactions with N2, H2, HCl, CCl4, and CO are described. With CO the new cobalt(I) silyl [Co(SiF3)(CO)2L2] is formed. The stability of the silyls to loss of SiR3H decreases as the electronegativity of R decreases, which allows the less-stable complexes to participate in catalytic processes. The reaction of SiR3H with D2(R = F, OEt, Et, or Me), of SiH(OEt)3 or Me3Si[OSi(H)Me]nOSiMe3 with EtOH, and of SiH(OEt)3 with hex-1-ene are catalysed by [CoH(X2)L3] or by [CoH2{Si(OEt)3}L3]. The deuteriation reaction provide an easy routr to deuteriosilanes, SiR3D.