Abstract
The dicarbonyl(cyclopentadienyl)(phenylcarbyne)manganese cation, [(η 5-C 5H 5(CO) 2MnCPh] + ( 1), reacts with dimethyl cyanamide, Me 2NCN ( 2), to give the ansa-carbene complex ( 3) containing a chelating η 1,η 5-(dimethylamino)[(cyclopentadienyl)(phenyl)methyleneamino]carbene ligand. The reaction proceeds most likely by the sequence nucleophilic addition of 2 to the carbyne carbon of 1/1,3-migration of Cp(CO) 2Mn/electrophilic attack at the cyclopentadienyl ligand accompanied by CC coupling and proton elimination. In the reaction of [(η 5-C 5Me 5)(CO) 2MnCPh] + with 2 Me + is formally eliminated from the Cp★ ligand to form the ansa-carbene complex ( 6). [(η 5-C 5H 4Me)(CO) 2MnCPh] + reacts with 2 to give two isomeric ansa-carbene complexes ( 8a and 8b) in a ratio of 1/5. Both compounds are derived from proton abstraction from the ring. Me + elimination (to give 3) is not observed. The structures of the complexes 3 and 8b have been established by X-ray analyses.
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