METAL COMPLEXATION OF THIOACYLFERROCENES - CRYSTAL-STRUCTURES OF PENTACARBONYL(THIOBENZOYLFERROCENE-S)CHROMIUM AND BENZOYLFERROCENE

Acylferrocenes (C5H5)Fe(C5H4COR) (RCH3, C2H5, (CH3)2CH, (CH3)3C or Ph) can be readily thionated to give thioacylferrocenes by use of P4S10 in non-polar solvents such as CH2Cl2 or toluene; use of polar solvents such as THF or diglyme provides very poor conversions. Thiobenzoylferrocene reacts readily with Et4N+-[M(CO)5I]- (M = Cr, Mo, or W) in the presence of silver nitrate to yield (C5H5)Fe[C5H4CPh{SM(CO)5}], in which the M(CO)5 group is bonded to the sulphur atom as revealed by an X-ray diffraction study. The structure consists of isolated molecules in which a Cr(CO)5 fragment of approximate C4v symmetry is bonded via sulphur to the thioacylferrocene with an CrS bond length of 2.412(1) Å, an SC bond length of 1.667(2) Å and a C-S-Cr angle of 121.9(1)°. Photo oxidation of (C5H5)Fe[C5H4CPh{SM(CO)5}] yields benzoylferrocene the crystal structure of which was determined. © 1990.