Metal complexation of thioacylferrocenes: crystal structures of pentacarbonyl(thiobenzoylferrocene-S)chromium and benzoylferrocene

Article abstract of DOI:10.1016/0022-328X(90)85008-M

Acylferrocenes (C5H5)Fe(C5H4COR) (R=CH3, 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 = Cr, Mo, or W) in the presence of silver nitrate to yield (C5H5)Fe>, 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 C_4v symmetry is bonded via sulphur to the thioacylferrocene with an Cr-S bond length of 2.412(1) Angstroem, an S=C bond length of 1.667(2) Angstroem and a C-S-Cr angle of 121.9(1) deg.Photo oxidation of (C5H5)Fe> yields benzoylferrocene the crystal structure of which was determined.