TY - JOUR
T1 - Redox-Noninnocent Ligand-Supported Vanadium Catalysts for the Chemoselective Reduction of Câ• X (X = O, N) Functionalities
AU - Zhang, Guoqi
AU - Wu, Jing
AU - Zheng, Shengping
AU - Neary, Michelle C.
AU - Mao, Jincheng
AU - Flores, Marco
AU - Trovitch, Ryan J.
AU - Dub, Pavel A.
N1 - Funding Information:
We are grateful for financial support from the US National Science Foundation (NSF, CHE-1900500) for this work. We also acknowledge PSC-CUNY awards (61321-0049 and 62154-0050) and the Seed grant from the Office for Advancement of Research at John Jay College, the City University of New York. Additional support from the NSF (CHE-1464543 and CHE-1651686) is also acknowledged. Computations were performed by using the Darwin Computational Cluster at Los Alamos National Laboratory.
Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/9/25
Y1 - 2019/9/25
N2 - 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.
AB - 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.
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U2 - 10.1021/jacs.9b07062
DO - 10.1021/jacs.9b07062
M3 - Article
C2 - 31479257
AN - SCOPUS:85072628955
VL - 141
SP - 15230
EP - 15239
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 38
ER -