79043-47-3Relevant academic research and scientific papers
A new bridging ligand in dinuclear iron carbonyl species. Synthesis, properties, and X-ray structure determination of xanthate-Fe2(CO)6 complexes
Patin, Henri,Mignani, Gérard,Benoit, Alain,Le Marouille, Jean-Yves,Grandjean, Daniel
, p. 4351 - 4355 (2008/10/08)
The complexes μ-(alkoxymethanethione-C,S)-μ-(alkylthio)-1,1,1,2,2,2-hexacarbonyldiiron are obtained in good yield by reaction of O-alkyl S-alkyl dithiocarbonates (or xanthates) with diiron nonacarbonyl. These compounds were characterized by microanalysis and IR, 1H and 13C NMR, and mass spectroscopies. The structure of the complex obtained from O-(adamantylmethyl) S-methyl dithiocarbonate has been determined by single-crystal X-ray diffraction. The crystals are triclinic, space group P1, with Z = 2 and a = 7.765 (3) A?, b = 11.025 (2) A?, c = 14.155 (2) A?, α = 106.24 (4)°, β = 104.56 (4)°, and γ = 90.37 (2)°. A full-matrix least-squares method refined the structure to R = 0.033 from 2715 nonzero independent reflections. The structure shows that fragmentation of the ligand has occurred and that one iron atom has inserted into the carbon-sulfur single bond, giving rise to two orthogonal bridges made from the thiocarbonyl function and by the S-alkyl group. This unexpected behavior of the xanthate ligand provides a convenient route to dissymmetrically bridged diiron hexacarbonyl species where the carbon of the bridge presents a carbenic character in agreement with the 13C and X-ray data. Displacement of one or two carbonyls or removal of the O-alkyl group by a phosphorus ligand is also described, and the mass spectra of the complexes are discussed.
