REACTIONS OF SILANES WITH THE BINUCLEAR HYDRIDE [(PR(I)2PCH2CH2PPR(I)2)RH]2(MU-H)2 - CATALYTIC DEUTERIUM-EXCHANGE ON DIPHENYLSILANE AND X-RAY STRUCTURE OF [(PR(I)2PCH2CH2PPR(I)2)RH]2(MU-H)(MU-ETA-2-HSIPH2)

Stoichiometric reactions of diphenylsilane (H2SiPh2) with [(dippe)Rh]2(mu-H)2 (1; dippe = 1,2-bis(diisopropylphosphino)ethane) have produced the new compounds [(dippe)Rh]2(mu-H)(mu-eta-2-HSiPh2) (2) and [(dippe)-Rh]2(mu-SiPh2)2 (3). An X-ray structure determination of 2 indicates the presence of a three-center, two-electron Rh-Si-H interaction. Deuterium exchange and silicon-silicon coupling to give 1,1,2,2-tetraphenyldisilane are both observed for diphenylsilane in the presence of catalytic amounts of 1; the isolated silyl-dihydride complex 2 and the bis(silylene) derivative 3 are likely to be active in these catalytic cycles.