Reactions of vinylidene and allenylidene cymantrene derivatives with isonitriles

Abstract

Isocyanides (RNC) insert into the MC bond in Cp(OC) 2MnCCHPh (I), to give the intermediates Cp(OC) 2Mn(RNCCHPh), R = t-Bu (II), C 6H 11 (III), CH 2Ph (IV). The reaction of II–IV with H 2O gives Cp(OC) 2Mn[π- cis- Ph(H)CC(H)C(O)NHR], R = t-Bu (V), C 6H 11 (VI), CH 2Ph (VII). Reaction of III with Et 2NH forms Cp(OC) 2Mn[π-Ph(H)CCC(NEt 2)NHC 6H 11], which upon reaction with H 2O yields VI. The possibility of eliminating π-olefin ligands from V or VII by reaction with n-donors (Py, PPh 3) is shown. Reaction of Cp(OC) 2MnCCCPh 2 (VIII) with t-BuNC gives Cp(OC) 2Mn[π-Ph 2CCCHC- (O)NH-t-Bu] (IX).