Synthesis and structural characterization of heterocyclic thiocarbene, selenocarbene, thione, and selone complexes of tungsten pentacarbonyl or chromium pentacarbonyl

Article abstract of DOI:10.1021/om00098a024

Various pentacarbonyl complexes of W and Cr containing heterocyclic ligands were prepared from the synthon formed by the addition of PhC≡CXLi (X = S or Se) to carbene complexes [M(CO)₅{(C(OEt)Ph}] (M = Cr, W). The nature of the electrophile (S or Se) that was added, as well as the temperature at which the reaction was carried out, determined whether the synthon acted mainly as an anionic thio- or selenocarbene complex to give rise to carbene complexes [W(CO)₅L] (L = CC(Ph)=C(Ph)SeS, CC(Ph)-=C(Ph)SSe, CC(Ph)=C (Ph)SeSe) or as a thio- or selenoacyl anion to form thione or selone complexes [Cr(CO)₅{S=CC(Ph)=C(Ph)SS}] and [W(CO)₅L] (L = S=CC(Ph)=C(Ph)SS, Se=CC(Ph)=C(Ph)SS, Se=CC(Ph)=C(Ph)SeSe).