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

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 V III complexes that feature a π-radical monoanionic 2,2':6',2"-terpyridine ligand (Rtpy ) functionalized at the 4'-position (R = (CH 3) 3SiCH 2, C 6H 5) catalyze mild and chemoselective hydroboration and hydrosilylation of functionalized ketones, aldehydes, imines, esters, and carboxamides with turnover numbers (TONs) of up to ~1000 and turnover frequencies (TOFs) of up to ~500 h –1. In conclusion, computational evaluation of the precatalyst synthesis and activation has revealed underappreciated complexity associated with the redox-active tpy chelate.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [5]; ORCiD logo [5]; ORCiD logo [6]
  1. The Graduate Center of City Univ. of New York, New York, NY (United States)
  2. The Graduate Center of City Univ. of New York, New York, NY (United States); City Univ. of New York, New York, NY (United States)
  3. City Univ. of New York, New York, NY (United States)
  4. Southwest Petroleum Univ., Sichuan (People’s Republic of China)
  5. Arizona State Univ., Tempe, AZ (United States)
  6. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1570623
Report Number(s):
LA-UR-19-22935
Journal ID: ISSN 0002-7863
Grant/Contract Number:  
89233218CNA000001
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 141; Journal Issue: 38; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Inorganic and Physical Chemistry; Organic Chemistry

Citation Formats

Zhang, Guoqi, Wu, Jing, Zheng, Shengping, Neary, Michelle C., Mao, Jincheng, Flores, Marco, Trovitch, Ryan J., and Dub, Pavel A. Redox-Noninnocent Ligand-Supported Vanadium Catalysts for the Chemoselective Reduction of C=X (X = O, N) Functionalities. United States: N. p., 2019. Web. doi:10.1021/jacs.9b07062.
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 C=X (X = O, N) Functionalities. United States. doi:10.1021/jacs.9b07062.
Zhang, Guoqi, Wu, Jing, Zheng, Shengping, Neary, Michelle C., Mao, Jincheng, Flores, Marco, Trovitch, Ryan J., and Dub, Pavel A. Tue . "Redox-Noninnocent Ligand-Supported Vanadium Catalysts for the Chemoselective Reduction of C=X (X = O, N) Functionalities". United States. doi:10.1021/jacs.9b07062. https://www.osti.gov/servlets/purl/1570623.
@article{osti_1570623,
title = {Redox-Noninnocent Ligand-Supported Vanadium Catalysts for the Chemoselective Reduction of C=X (X = O, N) Functionalities},
author = {Zhang, Guoqi and Wu, Jing and Zheng, Shengping and Neary, Michelle C. and Mao, Jincheng and Flores, Marco and Trovitch, Ryan J. and Dub, Pavel A.},
abstractNote = {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 π-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 ~1000 and turnover frequencies (TOFs) of up to ~500 h–1. In conclusion, computational evaluation of the precatalyst synthesis and activation has revealed underappreciated complexity associated with the redox-active tpy chelate.},
doi = {10.1021/jacs.9b07062},
journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 38,
volume = 141,
place = {United States},
year = {2019},
month = {9}
}

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Works referencing / citing this record:

1-D manganese( ii )-terpyridine coordination polymers as precatalysts for hydrofunctionalisation of carbonyl compounds
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