Monomeric three-coordinate N-heterocyclic carbene nickel(I) complexes

Synthesis, structures, and catalytic applications in cross-coupling reactions

Kouki Matsubara, Yukino Fukahori, Takahiro Inatomi, Saeko Tazaki, Yuji Yamada, Yuji Koga, Shinji Kanegawa, Toshikazu Nakamura

Research output: Contribution to journalArticle

19 Citations (Scopus)

Abstract

A series of three-coordinate monovalent nickel halide complexes bearing N-heterocyclic carbene (NHC) ligands, i.e., NiCl(IPr)(L) [L = pyridine, P(OPh)3, bis(diphenylphosphino)butane (dppb), IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene], NiX(IMes)(PPh3) (X = Cl and Br, IMes = 1,3-bis(mesityl)imidazol-2-ylidene), were prepared. The complexes were identified using NMR spectroscopy, superconducting quantum interference device (SQUID), and X-ray crystallography. Additionally, ESR spectra of NiCl(IPr)(pyridine) were taken in toluene. These complexes had three-coordinate Y-shaped geometries in both the solid and solution states. The compounds containing IPr showed equilibrium between the monomeric and dimeric forms, with liberation of ligands. Addition of 1,2-bis(diphenylphosphino)ethane and 1,3-bis(diphenylphosphino)propane to the dinickel(I) IPr complex instead of dppb resulted in heterolytic cleavage to nickel(0) and nickel(II) species. Catalysis of Suzuki cross-coupling and Buchwald-Hartwig amination of aryl bromide using the complexes was investigated. The efficiencies in the amination of aryl bromide depended strongly on the additional donor ligands.

Original languageEnglish
Pages (from-to)3281-3287
Number of pages7
JournalOrganometallics
Volume35
Issue number19
DOIs
Publication statusPublished - Oct 10 2016

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cross coupling
carbenes
Nickel
Amination
nickel
butanes
Ligands
Bromides
imidazoles
ligands
bromides
pyridines
Bearings (structural)
synthesis
X ray crystallography
SQUIDs
Toluene
propane
ethane
Catalysis

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Monomeric three-coordinate N-heterocyclic carbene nickel(I) complexes : Synthesis, structures, and catalytic applications in cross-coupling reactions. / Matsubara, Kouki; Fukahori, Yukino; Inatomi, Takahiro; Tazaki, Saeko; Yamada, Yuji; Koga, Yuji; Kanegawa, Shinji; Nakamura, Toshikazu.

In: Organometallics, Vol. 35, No. 19, 10.10.2016, p. 3281-3287.

Research output: Contribution to journalArticle

Matsubara, Kouki ; Fukahori, Yukino ; Inatomi, Takahiro ; Tazaki, Saeko ; Yamada, Yuji ; Koga, Yuji ; Kanegawa, Shinji ; Nakamura, Toshikazu. / Monomeric three-coordinate N-heterocyclic carbene nickel(I) complexes : Synthesis, structures, and catalytic applications in cross-coupling reactions. In: Organometallics. 2016 ; Vol. 35, No. 19. pp. 3281-3287.
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