Synthesis and characterization of coordinatively unsaturated nickel(ii) and manganese(ii) alkyl complexes supported by the hydrotris(3-phenyl-5-methylpyrazolyl)borate (TpPh,Me) ligand

Abstract

The synthesis of several nickel(II) and manganese(II) alkyl complexes supported by hydrotris(3-phenyl-5-methylpyrazolyl)borate (Tp(Ph,Me)) ligand is reported. The metal halide complexes Tp(Ph,Me)MnCl(CH3CN) (1) and Tp(Ph,Me)NiCl (4) were used as precursors for synthesis of Tp(Ph,Me)MnCH2Si(Me)3 (2), Tp(Ph,Me)MnCH2Ph (3), Tp(Ph,Me)NiCH2Si(Me)3 (5) and Tp(Ph,Me)NiCH2Ph (6). The resulting Mn(II) and Ni(II) alkyl complexes, 2-3 and 5-6, were characterized by X-ray crystallography, NMR spectroscopy, and FT-IR spectroscopy. X-ray crystallographic analysis revealed distorted tetrahedral geometries for complexes 2-3 and 5 with a κ(3)-Tp(Ph,Me). Complex 6, on the other hand, was found to have a distorted square planar geometry with κ(2)-Tp(Ph,Me) and an η(3)-benzyl ligand. Transformations of 4 and Tp(Ph,Me)CoCl (10) via treatment with NaN3 to yield Tp(Ph,Me)NiN3 (11), Tp(Ph,Me)CoN3 (12), along with the synthesis of (Tp(Ph,Me))2Ni (8) and Tp(Ph,Me)NiCl(3-Ph-5MepzH) (9) are also reported.