Preparation of Hybrid Bidentate Phosphine-Ligands by Reduction of Their Benzylphosphonium or Phenylphosphonium Salts - X-Ray Crystal-Structure of 2-Aminophenyltriphenylphosphonium Tetrachloronickelate(II)

Abstract

The 2-substituted phenylphosphine bidentate hybrid ligands, 2-aminophenyl-, 2-methylamino- phenyl-, 2-hydroxphenyl- and (2-amino-3-methylpheny1)- diphenylphosphine , (1a-d), respectively, and 2-aminophenylmethylphenylphosphine, (le), were synthesized by reduction of their phenylphosphoniurn halides, (2a-e)X (X = Cl or Br), with sodium naphthalenide in tetrahydrofuran at -68º, or electrochemically at a mercury cathode. The phosphonium salts were prepared by reaction of triphenylphosphine with aryl halide and anhydrous nickel halide at 200º. X-Ray diffraction of (2a)₂ [NiCl₄] showed it to have monoclinic space group P2₁/n, a 10.657(4), b 20.966(3), c 20.422(6) Å , β101.33(2) and Z4. The structure was refined by a full-matrix least-squares procedure to a final R 0.050 for 3534 reflections with I