Correction: Significant differences of monooxotungsten(IV) and dioxotungsten(VI) benzenedithiolates containing two intramolecular NH···S hydrogen bonds from molybdenum analogues.

摘要: A monooxotungsten(IV) benzenedithiolate complex containing two intramolecular NH⋯S hydrogen bonds, (NEt4)2[WIVO(1,2-S2-3-t-BuNHCOC6H3)2] (1-W), was synthesized via a ligand-exchange reaction between new starting complex, (NEt4)2[WIVO(SC6F5)4], and partially deprotonated dithiol. When dithiol used in solution, the oxo ligand protonated removed to afford (NEt4)2[WIV(1,2-S2-3-t-BuNHCOC6H3)3]. The trans isomer, trans-1-W, crystallized, molecular structure determined X-ray analysis. Trans-1-W gradually isomerized by heating it solution eventually achieved an approximately 1 : 1 mixture of trans/cis isomers after 48 days. However, slightly excess amount isomer remained, so isomerization rate considerably slower than that molybdenum analogue. In presence NEt4BH4, deuteration NH protons observed acetonitrile-d3. oxidation both trans- cis-1-W Me3NO afforded corresponding dioxotungsten(VI) (NEt4)2[WVIO2(1,2-S2-3-t-BuNHCOC6H3)2] (2-W), as single isomer. contributions bonds bond distances, vibrational data, electrochemical properties are described comparisons with their analogues. results this comparative study yielded insights into tungsten enzymes.