Nonsymmetrical Benzene-Pyridine-Based Nickel Pincer Complexes Featuring Borohydride, Formate, Ethyl, and Nitrosyl Ligands

Nonsymmetrical nickel PCN pincer complexes [Ni((PCNX)-P-iPr)Cl] (X = NMe, CH2) are obtained by metalation of the benzene-pyridine-based pincer ligand (PCNX)-P-iPr (X = NMe, CH2) with [Ni(dme)Cl-2] (dme = 1,2-dimethoxyethane). These nickel species afforded the respective borohydride and ethyl complexes [Ni((PCNX)-P-iPr)-L] (L = BH4, Et) upon treatment with NaBH4 and EtMgBr (or Et2Mg), respectively. Reacting [Ni((TCNX)-T-iPr)(kappa(2)-BH4)] with CO2 gave the formate complexes [Ni((TCNX)-T-iPr)(OCHO)]. Treatment of [Ni((PCNX)-P-iPr)Cl] with the nitrosyl salt NOBF4 led to the formation of the unusual cationic square-pyramidal nickel nitrosyl pincer complexes [Ni((PCNX)-P-iPr)(NO)Cl](+) featuring a strongly bent NO ligand (angle Ni-N-O 128.5 degrees). These systems can be described as {NiNO}(10) according to the Enemark-Feltham convention. Despite of the bent nature of the NO ligand the nu(NO) is observed at 1849 cm(-1) which is more typical for a linear Ni-N-O arrangement. The structure of these complexes is rationalized by means of DFT calculations. The molecular structures of representative complexes are presented.