Accessing Pincer Bis(carbene) Ni(IV) Complexes from Ni(II) via Halogen and Halogen Surrogates

Gabriel Espinosa Martinez; Cristian Ocampo; Yun Ji Park; Alison R. Fout

doi:10.1021/jacs.5b12827

Accessing Pincer Bis(carbene) Ni(IV) Complexes from Ni(II) via Halogen and Halogen Surrogates

Gabriel Espinosa Martinez, Cristian Ocampo, Yun Ji Park, Alison R. Fout

Chemistry

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

Abstract

This communication describes the two-electron oxidation of (^DIPPCCC)NiX (^DIPPCCC = bis(diisopropylphenyl-benzimidazol-2-ylidene)phenyl); X = Cl or Br) with halogen and halogen surrogates to form (^DIPPCCC)NiX₃. These complexes represent a rare oxidation state of nickel, as well as an unprecedented reaction pathway to access these species through Br₂ and halogen surrogate (benzyltrimethylammonium tribromide). The Ni^IV complexes have been characterized by a suite of spectroscopic techniques and can readily reduce to the Ni^II counterpart, allowing for cycling between the Ni^II/Ni^IV oxidation states.

Original language	English (US)
Pages (from-to)	4290-4293
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	138
Issue number	13
DOIs	https://doi.org/10.1021/jacs.5b12827
State	Published - Apr 20 2016

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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10.1021/jacs.5b12827

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title = "Accessing Pincer Bis(carbene) Ni(IV) Complexes from Ni(II) via Halogen and Halogen Surrogates",

abstract = "This communication describes the two-electron oxidation of (DIPPCCC)NiX (DIPPCCC = bis(diisopropylphenyl-benzimidazol-2-ylidene)phenyl); X = Cl or Br) with halogen and halogen surrogates to form (DIPPCCC)NiX3. These complexes represent a rare oxidation state of nickel, as well as an unprecedented reaction pathway to access these species through Br2 and halogen surrogate (benzyltrimethylammonium tribromide). The NiIV complexes have been characterized by a suite of spectroscopic techniques and can readily reduce to the NiII counterpart, allowing for cycling between the NiII/NiIV oxidation states.",

author = "Martinez, {Gabriel Espinosa} and Cristian Ocampo and Park, {Yun Ji} and Fout, {Alison R.}",

note = "Funding Information: The authors thank Dr. Jeffery A. Bertke for assisting with crystallography and the NSF for financial support with a CAREER award (13151961) to A.R.F. The authors would like to thank Dr. Ellen Matson for help with electrochemistry and Abdulrahman Ibrahim for insightful discussions. Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

year = "2016",

month = apr,

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doi = "10.1021/jacs.5b12827",

language = "English (US)",

volume = "138",

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journal = "Journal of the American Chemical Society",

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T1 - Accessing Pincer Bis(carbene) Ni(IV) Complexes from Ni(II) via Halogen and Halogen Surrogates

AU - Martinez, Gabriel Espinosa

AU - Ocampo, Cristian

AU - Park, Yun Ji

AU - Fout, Alison R.

N1 - Funding Information: The authors thank Dr. Jeffery A. Bertke for assisting with crystallography and the NSF for financial support with a CAREER award (13151961) to A.R.F. The authors would like to thank Dr. Ellen Matson for help with electrochemistry and Abdulrahman Ibrahim for insightful discussions. Publisher Copyright: © 2016 American Chemical Society.

PY - 2016/4/20

Y1 - 2016/4/20

N2 - This communication describes the two-electron oxidation of (DIPPCCC)NiX (DIPPCCC = bis(diisopropylphenyl-benzimidazol-2-ylidene)phenyl); X = Cl or Br) with halogen and halogen surrogates to form (DIPPCCC)NiX3. These complexes represent a rare oxidation state of nickel, as well as an unprecedented reaction pathway to access these species through Br2 and halogen surrogate (benzyltrimethylammonium tribromide). The NiIV complexes have been characterized by a suite of spectroscopic techniques and can readily reduce to the NiII counterpart, allowing for cycling between the NiII/NiIV oxidation states.

AB - This communication describes the two-electron oxidation of (DIPPCCC)NiX (DIPPCCC = bis(diisopropylphenyl-benzimidazol-2-ylidene)phenyl); X = Cl or Br) with halogen and halogen surrogates to form (DIPPCCC)NiX3. These complexes represent a rare oxidation state of nickel, as well as an unprecedented reaction pathway to access these species through Br2 and halogen surrogate (benzyltrimethylammonium tribromide). The NiIV complexes have been characterized by a suite of spectroscopic techniques and can readily reduce to the NiII counterpart, allowing for cycling between the NiII/NiIV oxidation states.

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JF - Journal of the American Chemical Society

IS - 13

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Accessing Pincer Bis(carbene) Ni(IV) Complexes from Ni(II) via Halogen and Halogen Surrogates

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