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 journalArticle

Abstract

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
Pages (from-to)15230-15239
Number of pages10
JournalJournal of the American Chemical Society
Volume141
Issue number38
DOIs
Publication statusPublished - Sep 25 2019

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Hydrosilylation
Vanadium
Imines
Steel
Ketones
Aldehydes
Catalysis
Oxidation-Reduction
Esters
Chemical activation
Ligands
Oxidation
Catalysts
oligomycin sensitivity-conferring protein

ASJC Scopus subject areas

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

Cite this

Redox-Noninnocent Ligand-Supported Vanadium Catalysts for the Chemoselective Reduction of Câ• X (X = O, N) Functionalities. / Zhang, Guoqi; Wu, Jing; Zheng, Shengping; Neary, Michelle C.; Mao, Jincheng; Flores, Marco; Trovitch, Ryan J.; Dub, Pavel A.

In: Journal of the American Chemical Society, Vol. 141, No. 38, 25.09.2019, p. 15230-15239.

Research output: Contribution to journalArticle

Zhang, Guoqi ; Wu, Jing ; Zheng, Shengping ; Neary, Michelle C. ; Mao, Jincheng ; Flores, Marco ; Trovitch, Ryan J. ; Dub, Pavel A. / Redox-Noninnocent Ligand-Supported Vanadium Catalysts for the Chemoselective Reduction of Câ• X (X = O, N) Functionalities. In: Journal of the American Chemical Society. 2019 ; Vol. 141, No. 38. pp. 15230-15239.
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abstract = "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 {\"I}€-radical monoanionic 2,2′:6′,2″-terpyridine ligand (Rtpy{\^a}€¢)- 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 {\^a}¼1000 and turnover frequencies (TOFs) of up to {\^a}¼500 h-1. Computational evaluation of the precatalyst synthesis and activation has revealed underappreciated complexity associated with the redox-active tpy chelate.",
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