Co2(CO)8 and unsaturated epoxides as unexpected partners in generating functionalized siloxane oils and cross-linked materials

Herein, we describe the unexpected ring opening of the epoxide group of allyl glycidyl ether and 4-vinylcyclohexene oxide in polymethylhydrosiloxane (PMHS) hydrosilylation reaction using 0.1 mol% Co-2(CO)(8) as a catalyst. This results in the cross-linking of PMHS via newly formed Si-C, Si-O-C and Si-O-Si bonds. Our studies demonstrate the need for intramolecular proximity of Si-H bonds within the polysilane compound to trigger the cross-linking process. The catalytic system was also successfully employed for the synthesis of trifunctionalized cross-linked materials, demonstrating further the potential of using non-precious metal complexes in silicone chemistry for unprecedented reactivity.