NOVEL CLASS OF THIOKETONE COMPLEXES - CRYSTAL-STRUCTURE OF BIS(ETA-5-CYCLOPENTADIENYL)(THIOCAMPHOR)-TETRACARBONYLDIMOLYBDENUM

Diaryl, aralkyl, and cycloalkyl thioketones react with dicyclopentadienylhexacarbonyldimolybdenum or -ditungsten to give a new class of thione complexes. These complexes, of formula (R2CS)M2(CO)4(C5H4R')2 (M = Mo, W), can also be synthesized by a very facile reaction of thioketones with the metal-metal triple-bonded complexes [(C5H4R')M(CO)2]2. The structures of these organosulfur compounds were elucidated on the basis of elemental analyses and infrared and magnetic resonance (1H, 13C) data, as well as an X-ray analysis of the thiocamphor molybdenum complex. The X-ray analysis reveals novel bonding of the thioketone function, as well as the existence of one semibridging [Mo(1)-C(2)-0(2) angle of 161.9°] and three terminal carbonyl groups. The molybdenum-molybdenum bond distance is 3.145 Å. Several of the complexes undergo equilibration in solution. © 1979, American Chemical Society. All rights reserved.