Griffin Samuel E, Schafer Laurel L
Department of Chemistry, University of British Columbia (UBC), 2036 Main Mall, Vancouver, British Columbia V6T 1Z1, Canada.
Inorg Chem. 2020 Apr 20;59(8):5256-5260. doi: 10.1021/acs.inorgchem.0c00071. Epub 2020 Mar 28.
The reductive coupling of alcohols using vanadium pyridonate catalysts is reported. This attractive approach for C(sp)-C(sp) bond formation uses an oxophilic, earth-abundant metal for a catalytic deoxygenation reaction. Several pyridonate complexes of vanadium were synthesized, giving insight into the coordination chemistry of this understudied class of compounds. Isolated intermediates provide experimental mechanistic evidence that complements reported computational mechanistic proposals for the reductive coupling of alcohols. In contrast to previous mononuclear vanadium(V)/vanadium(III)/vanadium(IV) cycles, this pyridonate catalyst system is proposed to proceed by a vanadium(III)/vanadium(IV) cycle involving bimetallic intermediates.
报道了使用吡啶酸钒催化剂对醇进行还原偶联反应。这种用于形成C(sp)-C(sp)键的引人注目的方法使用了一种亲氧的、储量丰富的金属来进行催化脱氧反应。合成了几种钒的吡啶酸配合物，从而深入了解了这类研究较少的化合物的配位化学。分离出的中间体提供了实验机理证据，补充了已报道的关于醇还原偶联反应的计算机理推测。与之前的单核钒(V)/钒(III)/钒(IV)循环不同，该吡啶酸催化剂体系被认为是通过涉及双金属中间体的钒(III)/钒(IV)循环进行的。
