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Title: Redox chemistry and H-atom abstraction reactivity of a terminal zirconium( iv ) oxo compound mediated by an appended cobalt( i ) center

Abstract

The reactivity of the terminal ziroconium(IV) oxo complex, O≡Zr(MesNPiPr2)3CoCNtBu (2), is explored, revealing unique redox activity imparted by the pendent redox active cobalt(I) center. Oxo complex 2 can be chemically reduced using Na/Hg or Ph3C to afford the ZrIV/Co0 complexes [(µ-Na)OZr(MesNPiPr2)3CoCNtBu]2 (3) and Ph3COZr(MesNPiPr2)3CoCNtBu(4), respectively. Based on the cyclic voltammogram of 2, Ph3C ­should not be sufficiently reducing to achieve the chemical reduction of 2, but sufficient driving force for the reaction is provided by the nucleophilicity of the terminal oxo fragment and its affinity to bind Ph3C+. Accordingly, 2 reacts readily with [Ph3C][BPh4] and Ph3CCl to afford [Ph3COZr(MesNPiPr2)3CoCNtBu][BPh4]([5][BPh4])andPh3COZr(MesNPiPr2)3CoCl (6), respectively. The chemical oxidation of 2 is also investigated, revealing that oxidation of 2 is accompanied by immediate hydrogen atom abstraction from THF to afford the hydroxide complex [HOZr(MesNPiPr2)3CoCNtBu]+ ([9]+). Thus it is posited that the transient [OZr(MesNPiPr2)3CoCNtBu]+ [2]+ cation generated upon oxidation combines the basicity of a nucleophilic early metal oxo fragment with the oxidizing power of the appended cobalt center to facilitate H-atom abstraction.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [2];  [1]; ORCiD logo [1]
  1. Department of Chemistry and Biochemistry, The Ohio State University, Columbus, USA
  2. Department of Chemistry, University of Virginia, Charlottesville, USA
Publication Date:
Research Org.:
The Ohio State Univ., Columbus, OH (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1659344
Alternate Identifier(s):
OSTI ID: 1657788
Grant/Contract Number:  
SC0019179
Resource Type:
Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science Journal Volume: 11 Journal Issue: 39; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Zhang, Hongtu, Hatzis, Gregory P., Dickie, Diane A., Moore, Curtis E., and Thomas, Christine M.. Redox chemistry and H-atom abstraction reactivity of a terminal zirconium( iv ) oxo compound mediated by an appended cobalt( i ) center. United Kingdom: N. p., 2020. Web. https://doi.org/10.1039/D0SC04229C.
Zhang, Hongtu, Hatzis, Gregory P., Dickie, Diane A., Moore, Curtis E., & Thomas, Christine M.. Redox chemistry and H-atom abstraction reactivity of a terminal zirconium( iv ) oxo compound mediated by an appended cobalt( i ) center. United Kingdom. https://doi.org/10.1039/D0SC04229C
Zhang, Hongtu, Hatzis, Gregory P., Dickie, Diane A., Moore, Curtis E., and Thomas, Christine M.. Wed . "Redox chemistry and H-atom abstraction reactivity of a terminal zirconium( iv ) oxo compound mediated by an appended cobalt( i ) center". United Kingdom. https://doi.org/10.1039/D0SC04229C.
@article{osti_1659344,
title = {Redox chemistry and H-atom abstraction reactivity of a terminal zirconium( iv ) oxo compound mediated by an appended cobalt( i ) center},
author = {Zhang, Hongtu and Hatzis, Gregory P. and Dickie, Diane A. and Moore, Curtis E. and Thomas, Christine M.},
abstractNote = {The reactivity of the terminal ziroconium(IV) oxo complex, O≡Zr(MesNPiPr2)3CoCNtBu (2), is explored, revealing unique redox activity imparted by the pendent redox active cobalt(I) center. Oxo complex 2 can be chemically reduced using Na/Hg or Ph3C• to afford the ZrIV/Co0 complexes [(µ-Na)OZr(MesNPiPr2)3CoCNtBu]2 (3) and Ph3COZr(MesNPiPr2)3CoCNtBu(4), respectively. Based on the cyclic voltammogram of 2, Ph3C• ­should not be sufficiently reducing to achieve the chemical reduction of 2, but sufficient driving force for the reaction is provided by the nucleophilicity of the terminal oxo fragment and its affinity to bind Ph3C+. Accordingly, 2 reacts readily with [Ph3C][BPh4] and Ph3CCl to afford [Ph3COZr(MesNPiPr2)3CoCNtBu][BPh4]([5][BPh4])andPh3COZr(MesNPiPr2)3CoCl (6), respectively. The chemical oxidation of 2 is also investigated, revealing that oxidation of 2 is accompanied by immediate hydrogen atom abstraction from THF to afford the hydroxide complex [HOZr(MesNPiPr2)3CoCNtBu]+ ([9]+). Thus it is posited that the transient [OZr(MesNPiPr2)3CoCNtBu]+ [2]+ cation generated upon oxidation combines the basicity of a nucleophilic early metal oxo fragment with the oxidizing power of the appended cobalt center to facilitate H-atom abstraction.},
doi = {10.1039/D0SC04229C},
journal = {Chemical Science},
number = 39,
volume = 11,
place = {United Kingdom},
year = {2020},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
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https://doi.org/10.1039/D0SC04229C

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