The addition of PPh H, PPhMeH, PPhH , P(para-Tol)H , PMesH and PH to the two-coordinate Ni N-heterocyclic carbene species [Ni(NHC) ] (NHC=IiPr , IMe , IEt Me ) affords a series of mononuclear, terminal phosphido nickel complexes. Structural characterisation of nine of these compounds shows that they have unusual trans [H-Ni-PR ] or novel trans [R P-Ni-PR ] geometries. The bis-phosphido complexes are more accessible when smaller NHCs (IMe >IEt Me >IiPr ) and phosphines are employed. P-P activation of the diphosphines R P-PR (R =Ph , PhMe) provides an alternative route to some of the [Ni(NHC) (PR ) ] complexes. DFT calculations capture these trends with P-H bond activation proceeding from unconventional phosphine adducts in which the H substituent bridges the Ni-P bond. P-P bond activation from [Ni(NHC) (Ph P-PPh )] adducts proceeds with computed barriers below 10 kcal mol . The ability of the [Ni(NHC) ] moiety to afford isolable terminal phosphido products reflects the stability of the Ni-NHC bond that prevents ligand dissociation and onward reaction.

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http://www.ncbi.nlm.nih.gov/pmc/articles/PMC8518396PMC
http://dx.doi.org/10.1002/chem.202101484DOI Listing

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