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

doi:10.1021/jacs.9b07062

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

Molecular Sciences, School of (SMS)

Research output: Contribution to journal › Article › peer-review

47 Scopus citations

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 Ï€-radical monoanionic 2,2′:6′,2″-terpyridine ligand (Rtpy^â€¢)^- 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 language	English (US)
Pages (from-to)	15230-15239
Number of pages	10
Journal	Journal of the American Chemical Society
Volume	141
Issue number	38
DOIs	https://doi.org/10.1021/jacs.9b07062
State	Published - Sep 25 2019

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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10.1021/jacs.9b07062

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@article{347342219f6c4989874560aff272b662,

title = "Redox-Noninnocent Ligand-Supported Vanadium Catalysts for the Chemoselective Reduction of C{\^a}• 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 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.",

author = "Guoqi Zhang and Jing Wu and Shengping Zheng and Neary, {Michelle C.} and Jincheng Mao and Marco Flores and Trovitch, {Ryan J.} and Dub, {Pavel A.}",

note = "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: {\textcopyright} 2019 American Chemical Society.",

year = "2019",

month = sep,

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doi = "10.1021/jacs.9b07062",

language = "English (US)",

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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 (Rtpyâ€¢)- 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 (Rtpyâ€¢)- 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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ER -

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

Abstract

ASJC Scopus subject areas

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CCDC 1946740: Experimental Crystal Structure Determination

CCDC 1590117: Experimental Crystal Structure Determination

CCDC 1937659: Experimental Crystal Structure Determination

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

Abstract

ASJC Scopus subject areas

Access to Document

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Datasets

CCDC 1946740: Experimental Crystal Structure Determination

CCDC 1590117: Experimental Crystal Structure Determination

CCDC 1937659: Experimental Crystal Structure Determination

Cite this