MIXED-LIGAND COMPLEXES OF RHENIUM .4. THE REACTION OF [RENCL2(ME2PHP)3] WITH DITHIOCARBAMATES - X-RAY CRYSTAL-STRUCTURES OF TRANS-CHLORO-DIMETHYLDITHIOCARBAMATO-BIS(DIMETHYLPHENYLPHOSPHINE)NITRIDORHENIUM(V), [REN(CL)(ME2PHP)2(ME2DTC)], AND BIS(DIETHYLDITHIOCARBAMATO)-(DIMETHYLPHENYLPHOSPHINE)NITRIDORHENIUM(V), [REN(CL)(ME2PHP)(ET2DTC)2]

[ReNCl2(Me2PhP)3] reacts with dialkyldithiocarbamates, R2dtc-, under a stepwise ligand exchange. Final products of these reactions are the well-known [ReN(R2dtc)2] bischelates. Intermediatelly, however, complexes of the general formulae [ReN(Cl)(Me2PhP)2(R2dtc)] and [ReN(Me2PhP)(R2dtC)2] can be isolated. Representatives have been structurally characterized. [ReN(Cl)(Me2PhP)2(Me2dtc)] crystallizes monoclinic in the space group P2(1)/c, Z = 4. The dimensions of the unit cell are a = 13.071(3); b = 11.622(1); c = 15.667(3) angstrom; beta = 97.09(1)degrees. The rhenium atom has a distorted octahedral environment; the Re=N bond length is 1.71(1) angstrom. The Re-Cl bond distance is markedly lengthened (2.665(2) angstrom) as a consequence of the strong trans labilizing influence of the coordinated nitrido ligand. [ReN(Me2PhP)(Et2dtc)2] crystallizes monoclinic in the space group P2(1)/c, Z = 4, a = 17.262(3); b = 14.915(2); c = 9.888(2); beta = 76.35(8)degrees. The equatorial coordination sphere is occupied by one phosphorus atom and three sulphur atoms. One of the dithiocarbamate ligands is coordinated bidentately; the second one with two distinct Re-S bond lengths. The Re-S(4) distance is 2.7983(2) angstrom which can be discussed as a weak interaction with the metal.