title: Reactions of phenylacetylene with nickel POCOP-pincer hydride complexes resulting in different outcomes from their palladium analogues.
abstract: Nickel POCOP-pincer hydride complexes [2,6-(R2PO)2C6H3]NiH (R = (I)Pr, 4a; R = (c)Pe = cyclopentyl, 4b) react with phenylacetylene to generate [2,6-(R2PO)2C6H3]NiC(Ph)=CH2 (5a–b) as the major product and (E)-[2,6-(R2PO)2C6H3]NiCH=CHPh (6a–b) as the minor product. The 2,1-insertion is more favorable than the 1,2-insertion and both pathways involve cis addition of Ni–H across the C≡C bond. Unlike the palladium case, alkynyl complexes [2,6-(R2PO)2C6H3]NiC≡CPh (7a–b) and H2 are not produced in the nickel system. The more bulky hydride complex [2,6-((t)Bu2PO)2C6H3]NiH (4c) shows no reactivity towards phenylacetylene. Catalytic hydrogenation of phenylacetylene with 4a–b takes place at an elevated temperature (70–100 °C) and proves to be heterogeneous. The structures of 5b, 6a, 7a and 7b have been studied by X-ray crystallography.
authors.affiliation: Department of Chemistry, University of Cincinnati, P. O. Box 210172, Cincinnati, Ohio 45221-0172, USA. hairong.guan@uc.edu.
authors.forename: Gleason L O
authors.initials: GL
authors.lastname: Wilson
authors.forename: Medhanei
authors.initials: M
authors.lastname: Abraha
authors.forename: Jeanette A
authors.initials: JA
authors.lastname: Krause
authors.forename: Hairong
authors.initials: H
authors.lastname: Guan