4.5 Article

Synthesis and Structural Characterization of Half-Sandwich Nickel Complexes Bearing Two Different N-Heterocyclic Carbene Ligands

Journal

ORGANOMETALLICS
Volume 30, Issue 24, Pages 6685-6691

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/om200864z

Keywords

-

Funding

  1. Ministere de l'Enseignement Superieur et de la Recherche
  2. CNRS
  3. University of Strasbourg

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Cationic cyclopentadienyl mixed bis-N-heterocyclic carbene (NHC) nickel complexes of the general formula [Ni(NHC)(NHC')Cp](PF6) (NHC/NHC' = 1,3-bis(2,4,6- trimethylphenyl)imidazol-2-ylidene (Mes(2)NHC) a, 1,3-dimethyl-imidazol-2-ylidene (Me2NHC) b, 1-isopropyl-3-methyl-imidazol-2-ylidene (iPr-NHC-Me) c; Cp = eta(5)-C5H5) were prepared by the reaction of the cationic monocarbene complex [Ni(Mes(2)NHC)-(NCMe)Cp](PF6) 1a or [Ni(Me2NHC)(NCMe)Cp](BF4) 1b with the appropriate free carbene. The new mixed bis(carbene) complexes [Ni(Mes(2)NHC)(Me2NHC)Cp](PF6) 2ab, [Ni(Mes(2)NHC)(iPr-NHC-Me)Cp](PF6) 2ac, and [Ni(Me2NHC)(iPr-NHC-Me)CpRBF4) 2bc were obtained in moderate-to-high yields and were fully characterized by H-1 and C-13 NMR spectroscopies, elemental analyses, and, in the case of 2ab, by a single-crystal X-ray diffraction study. The monocarbene precursor 1b was also structurally characterized. The mixed bis-NHC complexes 2ab and 2ac were tested as catalysts for the Suzuki-Miyaura cross-coupling of phenylboronic acid with 4'-bromoacetophenone, and their activities were compared to that of related monocarbene CpNi complexes.

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