Fischer aminocarbene conformers containing a 2-thienyl or 2-furyl ring: a crystallographic, NMR, and DFT study.

Fischer aminocarbene complexes [(CO)5M=C(NHR)Y] (M=Cr or W; R=H, Cy or C2H4NH2; Y=2-thienyl or 2-furyl) containing an amino group exist as two isomers in solution, theEandZisomers. The two isomers arise from restricted rotation about the N–Ccarbenebond, that exhibits double bond character due toπ-donation from nitrogen to the carbene carbon. Each isomer exists as two conformers in fast equilibrium with each other. The conformers arise from the rotation of the aryl ring around the Ccarbene–Carylsingle bond with a DFT calculated rotation barrier of 0.1–0.5 eV. The main isomer, isolated in the solid state, generally exhibits asynorientation of the aryl ring relative to the amino substituent and aZconfiguration of the amino substituent relative to the metal. [ABSTRACT FROM PUBLISHER]