Reactions of transition metal thiolato units IV.: Formation of phosphine-containing cobalt or nickel complexes with iso-maleonitrile-dithiolate

The reaction of M2+ (M=Co or Ni) with K-2(i-mnt) and phosphine forms chelated ternary coordination compounds (1)-(4). The crystal structures of Ni(i-mnt)(dppmSe) (1) (in the presence of Se) and ((Bu4N)-Bu-n)[Co(i-mnt)(2)(PBu3n)(2)] (2) were determined by single-crystal X-ray diffraction analyses; (1) crystallizes in the monoclinic space group P2(1)/n with a=12.002(3), b=19.568(11), c=12.456(5) Angstrom, beta=92.22(3)degrees, V=2923.4 Angstrom(3), Z=2, R (R-w)=0.051 (0.062). The distorted, square planar Ni atom Forms two individual chelate rings with the two bidentate ligands. Complex (2) crystallizes in space group <P(1)over bar> with a=10.682(2), b=28.496(6), c=9.959(2)Angstrom, alpha=91.31(2), beta=97.71(2), gamma=83.68(2)degrees, V=2986(1) Angstrom(3), Z=2, R (R-w)=0.060 (0.072). The octahedral Co(III) ion in (2) has an elongated structure with two monodentate phosphines in axial positions and i-mnt groups chelating in the equatorial plane. Spectroscopic characterization was performed where appropriate.