PREPARATION OF HYBRID BIDENTATE PHOSPHINE-LIGANDS BY REDUCTION OF THEIR BENZYLPHOSPHONIUM OR PHENYLPHOSPHONIUM SALTS - X-RAY CRYSTAL-STRUCTURE OF 2-AMINOPHENYLTRIPHENYLPHOSPHONIUM TETRACHLORONICKELATE(II)

The 2-substituted phenylphosphine bidentate hybrid ligands, 2-aminophenyl-, 2-methylaminophenyl-, 2-hydroxphenyl- and (2-amino-3-methylphenyl)-diphenylphosphine, (1a-d), respectively, and 2-aminophenylmethylphenylphosphine, (1e), were synthesized by reduction of their phenylphosphonium halides, (2a-e)X (X = Cl or Br), with sodium naphthalenide in tetrahydrofuran at -68-degrees, or electrochemically at a mercury cathode. The phosphonium salts were prepared by reaction of triphenylphosphine with aryl halide and anhydrous nickel halide at 200-degrees. X-Ray diffraction of (2a)2 [NiCl4] showed it to have monoclinic space group P2(1)/n, a 10.657(4), b 20.966(3), c 20.422(6) angstrom, beta 101.33(2)-degrees and Z4. The structure was refined by a full-matrix least-squares procedure to a final R 0.050 for 3534 reflections with I greater-than-or-equal-to 2.5-sigma(I)