Highly nucleophilic acetylide, vinyl, and vinylidene complexes. Final progress report, 1 January 1991--31 March 1994

摘要

In the course of this research the authors found that the anionic alkynyl complex (Cp(prime)(CO)(PPh(sub 3))Mn-C(triple bond)C-CH(sub 3))(sup (minus)) can be generated in situ by the addition of two equivalents of n-BuLi to a solution of the carbene complex Cp(prime)(CO)(PPh(sub 3))Mn(double bond)C(OMe)CH(sub 2)CH(sub 3). It was also found that the highly nucleophilic propynyl complex (Cp(CO)(PPh(sub 3))Mn-C(triple bond)C-Me)(sup (minus)) reacts with a variety of aldehydes and ketones in the presence of BF(sub 3)(center dot)Et(sub 2)O to give, after quenching with MeOH, a series of cationic vinylcarbyne complexes of the general form (Cp(CO)(PPh(sub 3))Mn(triple bond)C-C(Me)(double bond)C(R)(R(prime)))BF(sub 4). The cationic alkylidyne complexes (Cp(CO)(sub 2)M(triple bond)C-CH(sub 2)R)(sup +) (M = Re, R = H, M = Mn, R = H, Me, Ph) have been found to undergo facile deprotonation to give the corresponding neutral vinylidene complexes Cp(CO)(sub 2)M(double bond)C(double bond)C(H)R. The authors have also investigated reactions relevant to the halide promoted Fe and Ru catalyzed carbonylation of nitroaromatics. The final part of this work has involved investigations of metal-oxo complexes.