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Synthesis, Characterization, and Catalytic Activity of Ni(II) Alkyl Complexes Supported by Pyrrole-Diphosphine Ligands.


ABSTRACT: The organometallic Ni(II) chemistry of the pyrrole-based pincer ligands, (P2RPyr)- (P2RPyr = 2,5-(R2PCH2)2C4H2N, R = Ph or Cy) is reported. Reactions of Grignard reagents with [NiCl(P2R Pyr)] afford a variety of alkyl and aryl complexes (methyl, ethyl, benzyl, phenyl, and allyl) that all display square planar geometries about nickel. The hydride complex, [NiH(P2CyPyr)], can also prepared either through treatment of [NiCl(P2CyPyr)] with LiHBEt3, or by reaction of H(P2RPyr) with [Ni(COD)2] (COD = 1,4-cyclooctadiene). Reactions of the methyl and hydride complexes with CO and CO2, respectively, evince clean migratory insertion chemistry of the Ni-C and Ni-H bonds. Both the alkyl and chloride complexes are active catalysts for the Kumada coupling of aryl chlorides and aryl or alkyl Grignard reagents at room temperature. The solid-state structures of several of the complexes are reported.

SUBMITTER: Venkanna GT 

PROVIDER: S-EPMC3931010 | biostudies-literature | 2013 Aug

REPOSITORIES: biostudies-literature

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Synthesis, Characterization, and Catalytic Activity of Ni(II) Alkyl Complexes Supported by Pyrrole-Diphosphine Ligands.

Venkanna Gopaladasu T GT   Tammineni Swetha S   Arman Hadi D HD   Tonzetich Zachary J ZJ  

Organometallics 20130801 16


The organometallic Ni(II) chemistry of the pyrrole-based pincer ligands, (P<sub>2</sub><sup>R</sup>Pyr)<sup>-</sup> (P<sub>2</sub><sup>R</sup>Pyr = 2,5-(R<sub>2</sub>PCH<sub>2</sub>)<sub>2</sub>C<sub>4</sub>H<sub>2</sub>N, R = Ph or Cy) is reported. Reactions of Grignard reagents with [NiCl(P<sub>2</sub><sup>R</sup> Pyr)] afford a variety of alkyl and aryl complexes (methyl, ethyl, benzyl, phenyl, and allyl) that all display square planar geometries about nickel. The hydride complex, [NiH(P<sub>  ...[more]

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