Tetradecaisopropoxydihydridotetratungsten(IV). Oxidative addition of PrO-H across a tungsten-to-tungsten triple bond

Abstract : The title compound W4(OPr(1)) 14 (H)2 is formed in the reaction between W2(NMe2)6 and Pr(i)OH and has been characterized by a single crystal X-ray study. Formation of this novel tetranuclear complex is accounted for by the following sequence of reactions: (a) alcoholysis, W2 (NMe2)6 + 6PriOH yields W2(OPr(1))6 + 6HNMe2, (b) oxidative addition of Pr(i)O-H across a W=W, W2(OPr(i))6 + Pr(i)O-H yields W2(OPr(i))7(mu-H) W=W distance = 2.446(1) A and (c) association by PriO bridge formation, 2W2(OPr(i))7 (mu-H) yields W4 (OPr(i))14(H)2. (Author)