[Ni(NHC)2 ] as a Scaffold for Structurally Characterized trans [H-Ni-PR2 ] and trans [R2 P-Ni-PR2 ] Complexes.

The addition of PPh2 H, PPhMeH, PPhH2 , P(para-Tol)H2 , PMesH2 and PH3 to the two-coordinate Ni0 N-heterocyclic carbene species [Ni(NHC)2 ] (NHC=IiPr2 , IMe4 , IEt2 Me2 ) affords a series of mononuclear, terminal phosphido nickel complexes. Structural characterisation of nine of these compounds shows that they have unusual trans [H-Ni-PR2 ] or novel trans [R2 P-Ni-PR2 ] geometries. The bis-phosphido complexes are more accessible when smaller NHCs (IMe4 >IEt2 Me2 >IiPr2 ) and phosphines are employed. P-P activation of the diphosphines R2 P-PR2 (R2 =Ph2 , PhMe) provides an alternative route to some of the [Ni(NHC)2 (PR2 )2 ] 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)2 (Ph2 P-PPh2 )] adducts proceeds with computed barriers below 10 kcal mol-1 . The ability of the [Ni(NHC)2 ] moiety to afford isolable terminal phosphido products reflects the stability of the Ni-NHC bond that prevents ligand dissociation and onward reaction.