Nickel(II) pincer carbene complexes: Oxidative addition of an aryl C-H bond to form a Ni(II) hydride

Ellen M. Matson; Gabriel Espinosa Martinez; Abdulrahman D. Ibrahim; Bailey J. Jackson; Jeffrey A. Bertke; Alison R. Fout

doi:10.1021/om5007177

Nickel(II) pincer carbene complexes: Oxidative addition of an aryl C-H bond to form a Ni(II) hydride

Ellen M. Matson
, Gabriel Espinosa Martinez
, Abdulrahman D. Ibrahim
, Bailey J. Jackson
, Jeffrey A. Bertke
, Alison R. Fout

Chemistry

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

Abstract

The synthesis and characterization of a series of nickel(II) pincer complexes of the meta-phenylene-bridged bis-N-heterocyclic ^DIPPCCC ligand framework are reported. Characterization of the Ni(II)Cl complex revealed a square planar species with Cl^- and the anionic carbon trans to one another. Formation of Ni(II) alkyl complexes derived from complex 1 was accomplished by addition of LiR [R = CH₃ (2); CH₂SiMe₃ (3)]. Furthermore, we report a synthetic pathway to access the catalytically relevant Ni(II)H species (^DIPPCCC)NiH (4), by direct oxidative addition of an aryl C-H bond across a Ni(0) center. Complexes 1-4 have been characterized by ¹H and ¹³C NMR and electronic absorption spectroscopies as well as X-ray crystallography.

Original language	English (US)
Pages (from-to)	399-407
Number of pages	9
Journal	Organometallics
Volume	34
Issue number	2
DOIs	https://doi.org/10.1021/om5007177
State	Published - Jan 26 2015

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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10.1021/om5007177

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title = "Nickel(II) pincer carbene complexes: Oxidative addition of an aryl C-H bond to form a Ni(II) hydride",

abstract = "The synthesis and characterization of a series of nickel(II) pincer complexes of the meta-phenylene-bridged bis-N-heterocyclic DIPPCCC ligand framework are reported. Characterization of the Ni(II)Cl complex revealed a square planar species with Cl- and the anionic carbon trans to one another. Formation of Ni(II) alkyl complexes derived from complex 1 was accomplished by addition of LiR [R = CH3 (2); CH2SiMe3 (3)]. Furthermore, we report a synthetic pathway to access the catalytically relevant Ni(II)H species (DIPPCCC)NiH (4), by direct oxidative addition of an aryl C-H bond across a Ni(0) center. Complexes 1-4 have been characterized by 1H and 13C NMR and electronic absorption spectroscopies as well as X-ray crystallography.",

author = "Matson, \{Ellen M.\} and \{Espinosa Martinez\}, Gabriel and Ibrahim, \{Abdulrahman D.\} and Jackson, \{Bailey J.\} and Bertke, \{Jeffrey A.\} and Fout, \{Alison R.\}",

note = "Publisher Copyright: {\textcopyright} 2014 American Chemical Society.",

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doi = "10.1021/om5007177",

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T1 - Nickel(II) pincer carbene complexes

T2 - Oxidative addition of an aryl C-H bond to form a Ni(II) hydride

AU - Matson, Ellen M.

AU - Espinosa Martinez, Gabriel

AU - Ibrahim, Abdulrahman D.

AU - Jackson, Bailey J.

AU - Bertke, Jeffrey A.

AU - Fout, Alison R.

PY - 2015/1/26

Y1 - 2015/1/26

N2 - The synthesis and characterization of a series of nickel(II) pincer complexes of the meta-phenylene-bridged bis-N-heterocyclic DIPPCCC ligand framework are reported. Characterization of the Ni(II)Cl complex revealed a square planar species with Cl- and the anionic carbon trans to one another. Formation of Ni(II) alkyl complexes derived from complex 1 was accomplished by addition of LiR [R = CH3 (2); CH2SiMe3 (3)]. Furthermore, we report a synthetic pathway to access the catalytically relevant Ni(II)H species (DIPPCCC)NiH (4), by direct oxidative addition of an aryl C-H bond across a Ni(0) center. Complexes 1-4 have been characterized by 1H and 13C NMR and electronic absorption spectroscopies as well as X-ray crystallography.

AB - The synthesis and characterization of a series of nickel(II) pincer complexes of the meta-phenylene-bridged bis-N-heterocyclic DIPPCCC ligand framework are reported. Characterization of the Ni(II)Cl complex revealed a square planar species with Cl- and the anionic carbon trans to one another. Formation of Ni(II) alkyl complexes derived from complex 1 was accomplished by addition of LiR [R = CH3 (2); CH2SiMe3 (3)]. Furthermore, we report a synthetic pathway to access the catalytically relevant Ni(II)H species (DIPPCCC)NiH (4), by direct oxidative addition of an aryl C-H bond across a Ni(0) center. Complexes 1-4 have been characterized by 1H and 13C NMR and electronic absorption spectroscopies as well as X-ray crystallography.

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DO - 10.1021/om5007177

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SN - 0276-7333

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JO - Organometallics

JF - Organometallics

IS - 2

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Nickel(II) pincer carbene complexes: Oxidative addition of an aryl C-H bond to form a Ni(II) hydride

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