Base Metal-terpyridine Complex Immobilized on Stationary Phase Aimed as Reusable Hydrosilylation Catalyst.

The catalytic activity of a base metal-terpyridine complex immobilized on silica gel (M(tpy)X @SiO /H O: M=Mn, Fe, Co, Ni, Cu; X=Cl, Br) for hydrosilylation was investigated. Co(tpy)Br @SiO /H O in the presence of NaBHEt exhibited the highest catalytic activity for hydrosilylation of 1-octene with diphenylsilane (Ph SiH ) to form the anti-Markovnikov-type hydrosilylation compound as the main product. The reusability of Co(tpy)Br @SiO /H O activated by NaBHEt was examined. It was found that the catalytic activity decreased with repeated use because of the peeling off of the Co complex anchor portion from the silica gel surface upon the attack of NaBHEt . The introduction of Co(OAc) instead of CoBr to silica gel formed Co(tpy)(OAc) - and Co(tpy)(OH) -immobilized silica gel, which exhibited catalytic activity for the hydrosilylation in the absence of an activator such as NaBHEt . The glassware in which Co(tpy)(OH) was immobilized on the inner wall was prepared. It was found that the hydrosilylation catalytically occurred on the surface of a pretreated glassware and that the catalytic activity did not decrease even after 10 repeated uses.