The organometallic Ni(II) chemistry of the pyrrole-based pincer ligands, (P 2 R Pyr) − (P 2 R Pyr = 2,5-(R 2 PCH 2 ) 2 C 4 H 2 N, R = Ph or Cy) is reported. Reactions of Grignard reagents with [NiCl(P 2 R 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 2 Cy Pyr)], can also prepared either through treatment of [NiCl(P 2 Cy Pyr)] with LiHBEt 3 , or by reaction of H(P 2 R Pyr) with [Ni(COD) 2 ] (COD = 1,4-cyclooctadiene). Reactions of the methyl and hydride complexes with CO and CO 2 , 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.
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