THE REACTION OF TCCL3(ME2PHP)3 WITH DITHIO LIGANDS - SYNTHESIS, CHARACTERIZATION AND X-RAY CRYSTAL-STRUCTURES OF [TCCL2(ME2PHP)2(ME2DTP)] AND [TC(ME2PHP)(ETXAN)3], (ME2PHP = DIMETHYLPHENYLPHOSPHINE, ME2DTP- = O,O'-DIMETHYLDITHIOPHOSPHATE, ETXAN- = ETHYLXANTHATE)

Trichlorotris(dimethylphenylphosphine)technetium(III), [TcCl3(Me2PhP)3], reacts with dithio ligands to form chelate complexes of different compositions and coordination geometries. The reaction with ethylxanthate (Etxan-) yields the diamagnetic seven-coordinate [Tc(Me2PhP)(Etxan)3], which crystallizes monoclinic in the space group P2(1)/c with Z = 4 (a - 18.44(5), b = 9.2(l), c = 15.36(6) angstrom, beta = 104.3(2)-degrees). The final R value is 0.029. The metal has a pentagonal-bipyramidal environment. With ammonium dimethyldithiophosphate, (NH4)Me2dtp, [TcCl3(Me2Php)3] forms the paramagnetic [TcCl2(Me2PhP)2(Me2dtp)] in which the technetium atom has a distorted octahedral coordination sphere. The compound crystallizes orthorhombic, space group Pbcn, with Z = 4 (a = 16.207(l), b = 10.445(l), c = 14.878(l)). The final R value is 0.031. The chloro ligands are in trans arrangement.