Cyclometalation of Thiobenzophenones with Mononuclear Methyliron and ‐cobalt Complexes

Abstract

Abstract Under smooth conditions (–70 °C) thiobenzophenone derivatives react with [Fe(CH 3 ) 2 (PMe 3 ) 4 ] to form five‐membered metallacycles 1 and 2 by C–H activation. These complexes show octahedral coordination geometry; with [Co(CH 3 )(PMe 3 ) 4 ], complexes 3 and 4 with trigonal‐bipyramidal coordination are formed. Reaction with basic [Ni(CH 3 ) 2 (PMe 3 ) 3 ] causes reductive elimination (of ethane) with formation of zerovalent η 2 ‐C=S complexes 5 and 6 , possessing triangular‐planar coordination. The structures of the complexes were confirmed by X‐ray diffraction, and their coordination geometry is discussed.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)