Reactions of phenylacetylene with nickel POCOP-pincer hydride complexes resulting in different outcomes from their palladium analogues

Dalton Transactions : an International Journal of Inorganic Chemistry
Gleason L O WilsonHairong Guan

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.

References

Feb 22, 2007·Chemical Communications : Chem Comm·Valerica Pandarus, Davit Zargarian
Apr 20, 2007·Proceedings of the National Academy of Sciences of the United States of America·Maurice BrookhartGerard Parkin
Jun 15, 2010·Journal of the American Chemical Society·Sumit ChakrabortyHairong Guan
Jun 28, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Abderrahmen B Salah, Davit Zargarian
Aug 21, 2012·Journal of the American Chemical Society·Deven P EstesWesley Sattler
Feb 18, 2014·Angewandte Chemie·Jingjun HaoDavit Zargarian

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Citations

Jul 21, 2016·Chemical Reviews·Nathan A Eberhardt, Hairong Guan
Dec 20, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Thomas J MazzacanoNeal P Mankad
Jun 15, 2017·The Journal of Organic Chemistry·Justin B DiccianniTianning Diao

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