Synthesis, Characterization, and Reactivity of Nickel Hydride Complexes Containing 2,6-C6H3(CH2PR2)2 (R = tBu, cHex, and iPr) Pincer Ligands

The syntheses and full characterization of nickel hydrides containing the PCP pincer'-type ligand, where PCP = 2,6-C6H3(CH2PR2)(2) (R = tBu, cHex, and iPr), are reported. These Ni-H complexes are prepared by the conversion of ((PCP)-P-R)NiCl precursors into the corresponding nickel hydrides by use of appropriate hydride donors. Surprisingly, although the ((PCP)-P-R)NiCl precursors are quite similar chemically, the conversions to the hydrides were not straightforward and required different hydride reagents to provide analytically pure products. While NaBH4 was effective in the preparation of pure ((PCP)-P-tBu)NiH, Super-Hydride solution (LiEt3BH in THF) was required to prepare either ((PCP)-P-cHex)NiH or ((PCP)-P-iPr)NiH. Attempts to prepare a Ni-H from ((PCP)-P-Ph)NiCl with a variety of hydride reagents yielded only the free ligand as an identifiable product. Two of the derivatives, tBu and cHex, have also been subjected to single crystal X-ray analysis. The solid-state structures each showed a classic, near-square planar arrangement for Ni in which the PCP ligand occupied three meridional ligand points with the Ni-H trans to the Ni-C bond. The resulting Ni-H bond lengths were 1.42(3) and 1.55(2) angstrom for the tBu and cHex derivatives, respectively.