Patrick J. Lim, Damian A. Slizys, Jonathan M. White, Charles G. Young, Edward R.T. Tiekink
The reactions of Tp*W(S 2CNEt 2)(CO) 2 [Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate] with phenylacetylene, 2-butyne-1,4-diol, and dimethyl acetylenedicarboxylate (DMAC) in chlorinated solvents produce Tp*W(S 2CNEt 2-ηS)(η 2-PhC≡CH)(CO) (1), Tp*WCl(η 2-HOCH 2C≡CCH 2OH)(CO) (2), and Tp*W{OCC(CO 2Me)=C(CO 2Me)S -k3O,C,S)}(SCNEt 2-k2C,S) (3), respectively. The complexes have been characterized by microanalysis, IR and 1H and 13C NMR spectroscopy, mass spectrometry, and X-ray diffraction. Complexes 1 and 2 possess octahedral structures with aligned carbonyl and η 2-alkyne ligands (the latter occupying one coordination site) and a tridentate fac-Tp* ligand; the coordination spheres are completed by monodentate dithiocarbamate (W-S(1) 2.397(2) Å, W⋯S(2) 3.999(2) Å) and chloro ligands, respectively. Complex 3 contains a novel heterometallacycle incorporating acyl -k2O,C [≠(CO) 1585 cm -1; δc (C=O) 269.2, 1J cw 18 Hz] and enethiolate units, a thiocarboxamido ligand [≠(CN) 1525 cm -1; δc 250.3, 1J cw 81 Hz], and a tridentate fac-Tp* ligand. The complex exhibits an octahedral structure with planar, orthogonal acyl-enethiolate and thiocarboxamide ligands (the acyl and thiocarboxamide units each occupy one coordination site).
School of Chemistry, University of Melbourne, Victoria 3010, Australia; Department of Chemistry, National University of Singapore, Singapore 117543, Singapore; Chemistry Department, University of San Carlos, Cebu City 6000, Philippines
