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 [(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.
- 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. https://doi.org/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. https://doi.org/10.1021/acs.organomet.8b00687. https://www.osti.gov/servlets/purl/1487362.
@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 = {Wed Dec 05 00:00:00 EST 2018},
month = {Wed Dec 05 00:00:00 EST 2018}
}
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