Reactions of phenylacetylene with nickel POCOP-pincer hydride complexes resulting in different outcomes from their palladium analogues†
Nickel POCOP-pincer hydride complexes [2,6-(R2PO)2C6H3]NiH (R = iPr, 4a; R = cPe = 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]NiCHCHPh (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 CC bond. Unlike the palladium case, alkynyl complexes [2,6-(R2PO)2C6H3]NiCCPh (7a–b) and H2 are not produced in the nickel system. The more bulky hydride complex [2,6-(tBu2PO)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.
- This article is part of the themed collection: Earth Abundant Element Compounds in Homogeneous Catalysis