O-Alkylthiooxalato and dithiocarboxylato complexes of molybdenum and tungsten

Abstract The hydrosulfido complexes CpM(CO) 3 SH (M = Mo, W) react with one equivalent of O -alkyl oxalyl chlorides, RO 2 CCOCl, to form the corresponding O -alkylthiooxalato complexes CpM(CO) 3 SCOCO 2 R [M = Mo ( 1 ), W ( 2 ); R = Me ( a ), Et ( b )]. The reaction of the hydrosulfido complexes with half equivalent of oxalyl or succinyl chlorides produces the bimetallic complexes [CpM(CO) 3 SCO] 2 [M = Mo ( 3c ), W ( 4c )] and [CpM(CO) 3 SCOCH 2 ] 2 [M = Mo ( 3d ), W ( 4d )]. These new complexes have been characterized by elemental analysis, IR and 1 H NMR spectroscopy. The solid state structures of CpMo(CO) 3 SCOCO 2 CH 3 ( 1a ) and CpW(CO) 3 SCOCO 2 CH 2 CH 3 ( 2b ) were determined by X-ray crystal structure analysis.