Reactions of ruthenium cyclopropenyl complexes with trimethylsilyl azide

Abstract

Treatment of the phenyl substituted cyclopropenyl complex [Ru]–CC(Ph)CHPh (1a, [Ru] = (η⁵-C₅H₅)(PPh₃)₂Ru) with Me₃SiN₃ in THF in the presence of NH₄PF₆ at room temperature afforded the nitrile complex {[Ru]NCCH(Ph)CH₂Ph}PF₆5a. Similar reaction of the cyano substituted cyclopropenyl complex [Ru]–CC(Ph)CHCN 1b with Me₃SiN₃ gave the tetrazolate complex [Ru]–N₄CCH(Ph)CH₂CN 6. Proposals are made concerning the mechanism for the synthesis of these compounds. The reaction of [Ru]–CC(Ph)CHCHCH₂1c with Me₃SiN₃ takes a different route and gives the nitrile complex [Ru]–CN 7 and the five-membered-ring organic compound PhCCN₃HCH₂CH₃11. The structures of complexes 5a and 6 have been determined by single crystal X-ray diffraction analysis.