Redox-Noninnocent Ligand-Supported Vanadium Catalysts for the Chemoselective Reduction of Câ• X (X = O, N) Functionalities

Guoqi Zhang, Jing Wu, Shengping Zheng, Michelle C. Neary, Jincheng Mao, Marco Flores, Ryan J. Trovitch, Pavel A. Dub

Research output: Contribution to journalArticlepeer-review

47 Scopus citations


Catalysis is the second largest application for V after its use as an additive to improve steel production. Molecular complexes of vanadium(V) are particularly useful and efficient catalysts for oxidation processes; however, their ability to catalyze reductive transformations has yet to be fully explored. Here we report the first examples of polar organic functionality reduction mediated by V. Open-shell VIII complexes that feature a Ï€-radical monoanionic 2,2′:6′,2″-terpyridine ligand (Rtpy•)- functionalized at the 4′-position (R = (CH3)3SiCH2, C6H5) catalyze mild and chemoselective hydroboration and hydrosilylation of functionalized ketones, aldehydes, imines, esters, and carboxamides with turnover numbers (TONs) of up to â¼1000 and turnover frequencies (TOFs) of up to â¼500 h-1. Computational evaluation of the precatalyst synthesis and activation has revealed underappreciated complexity associated with the redox-active tpy chelate.

Original languageEnglish (US)
Pages (from-to)15230-15239
Number of pages10
JournalJournal of the American Chemical Society
Issue number38
StatePublished - Sep 25 2019

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry


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