Illusive tungsten-imido-dithiocarbamate complexes: Facile carbon–nitrogen bond formation
作者:Alexander Edwards、Graeme Hogarth、Nathan Hollingsworth、Joseph J. Oller
DOI:10.1016/j.inoche.2011.09.014
日期:2011.12
Heating [WO2(S2CNBu2i)(2)] with a slight excess of ArNCO (Ar=Ph, p-tolyl) results in the rapid formation of imido-ureato complexes [W(NAr)kappa(2)-ArNC(O)NAr}(S2CNBu2i)(2)], a transformation believed to occur via the bis (imido) intermediates [W(NAr)(2)(S2CNBu2i)(2)]. The ureato ligand is easily removed (as the urea) upon addition of gaseous HCl to afford the dichloride [W(NAr)Cl-2(S2CNBu2i)(2)]. While bis(imido) complexes are unavailable from the direct reaction of isocyanates (or amines) with [WO2(S2CNBu2i)(2)], they can be prepared upon addition of dithiocarbamate salts to [W(NBut)(2)(NHBut)(2)] addition of two equivalents of [NH2Bu2i][(Bu2NCS2)-N-i] affording [W(NBut)(2)(S2CNBu2i)(2)] in which both imido groups are linear. (C) 2011 Elsevier B.V. All rights reserved.