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Title: Investigation of Nitrile Hydration Chemistry by Two Transition Metal Hydroxide Complexes: Mn–OH and Ni–OH Nitrile Insertion Chemistry

Abstract

Herein we describe the synthesis of a series of nickel complexes, including the formation of [( iPrPN HP)Ni(PMe 3)][BPh 4] ( iPrPN HP = HN(CH 2CH 2(PiPr 2)) 2). The ability of this phosphine complex to perform the 1,2-addition of H 2O to produce the Ni–OH species [( iPrPN HP)NiOH][BPh 4] has been investigated. The nucleophilicity of the hydroxide moiety of both [(iPrPNHP)NiOH][BPh4] and the previously reported ( iPrPN HP)MnOH(CO) 2 was investigated through the hydration of aryl and alkyl nitriles, leading to the formation of a number of metal carboxamide (RC(O)NH–) bonds. This reactivity generated complexes with the general structures of [( iPrPN HP)Ni(NHC(O)R)][BPh 4] for nickel and ( iPrPN HP)Mn(NHC(O)R)(CO) 2 for manganese. Under catalytic conditions, the hydration of nitriles using nickel complexes yielded only a single turnover. However, ( iPrPN HP)MnOH(CO) 2 produced several turnovers, and the reaction conditions were probed for optimization.

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [1]
  1. 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 Office of Science (SC)
OSTI Identifier:
1487362
Report Number(s):
LA-UR-18-28930
Journal ID: ISSN 0276-7333
Grant/Contract Number:  
89233218CNA000001
Resource Type:
Accepted Manuscript
Journal Name:
Organometallics
Additional Journal Information:
Journal Volume: 37; Journal Issue: 24; Journal ID: ISSN 0276-7333
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Anderson, Nickolas H., Boncella, James M., and Tondreau, Aaron M. Investigation of Nitrile Hydration Chemistry by Two Transition Metal Hydroxide Complexes: Mn–OH and Ni–OH Nitrile Insertion Chemistry. United States: N. p., 2018. Web. doi:10.1021/acs.organomet.8b00687.
Anderson, Nickolas H., Boncella, James M., & Tondreau, Aaron M. Investigation of Nitrile Hydration Chemistry by Two Transition Metal Hydroxide Complexes: Mn–OH and Ni–OH Nitrile Insertion Chemistry. United States. doi:10.1021/acs.organomet.8b00687.
Anderson, Nickolas H., Boncella, James M., and Tondreau, Aaron M. Wed . "Investigation of Nitrile Hydration Chemistry by Two Transition Metal Hydroxide Complexes: Mn–OH and Ni–OH Nitrile Insertion Chemistry". United States. doi:10.1021/acs.organomet.8b00687.
@article{osti_1487362,
title = {Investigation of Nitrile Hydration Chemistry by Two Transition Metal Hydroxide Complexes: Mn–OH and Ni–OH Nitrile Insertion Chemistry},
author = {Anderson, Nickolas H. and Boncella, James M. and Tondreau, Aaron M.},
abstractNote = {Herein we describe the synthesis of a series of nickel complexes, including the formation of [(iPrPNHP)Ni(PMe3)][BPh4] (iPrPNHP = HN(CH2CH2(PiPr2))2). The ability of this phosphine complex to perform the 1,2-addition of H2O to produce the Ni–OH species [(iPrPNHP)NiOH][BPh4] has been investigated. The nucleophilicity of the hydroxide moiety of both [(iPrPNHP)NiOH][BPh4] and the previously reported (iPrPNHP)MnOH(CO)2 was investigated through the hydration of aryl and alkyl nitriles, leading to the formation of a number of metal carboxamide (RC(O)NH–) bonds. This reactivity generated complexes with the general structures of [(iPrPNHP)Ni(NHC(O)R)][BPh4] for nickel and (iPrPNHP)Mn(NHC(O)R)(CO)2 for manganese. Under catalytic conditions, the hydration of nitriles using nickel complexes yielded only a single turnover. However, (iPrPNHP)MnOH(CO)2 produced several turnovers, and the reaction conditions were probed for optimization.},
doi = {10.1021/acs.organomet.8b00687},
journal = {Organometallics},
number = 24,
volume = 37,
place = {United States},
year = {2018},
month = {12}
}

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This content will become publicly available on December 5, 2019
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