Abstract
Treatment of Tp(PPh3)2Ru−C⋮C−Ph (1) with ICH2CN affords the cationic vinylidene complex [Tp(PPh3)2RuCC(Ph)CH2CN]I (2). The neutral ruthenium cyclopropenyl complex (3) is then prepared by deprotonation of 2. Facile displacement of one phosphine ligand of 3 by CH3CN yields a diastereomeric mixture in a 4:1 ratio of the substitution product, (4). The cyclopropenyl ring in 3 and 4 is susceptible to ring opening by electrophiles such as CF3COOH, Ph3CPF6, and HgCl2. The substitution reaction of 3 with pyrazole is followed by an intramolecular nucleophilic addition of the nitrogen atom at the α-carbon atom to afford the metallacyclic complex, Tp(PPh3)Ru(C3H3NN)CC(Ph)CH2CN (8a). The reaction of 3 with CO in the presence of MeOH gives Tp(PPh3)(CO)RuC(OMe)C(Ph)CH2CN (9). The reaction of CF3COOH with 9 yields Tp(PPh3)(CO)RuC(O)CH(Ph)CH2CN (11). The structures of 8a and 11 have been determined by X-ray diffraction analysis.
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