MIXED-LIGAND COMPLEXES OF RHENIUM .6. SYNTHESIS AND X-RAY STRUCTURES OF THE RHENIUM THIONITROSYL COMPLEXES MER-[RE(NS)CL2(ME2PHP)3]CENTER-DOT-CH2CL2 AND TRANS-[RE(NS)CL3(ME2PHP)2]

mer-Dichlorotris(dimethylphenylphosphine)(thionitrosyl)rhenium(I), mer-[Re(NS)Cl2(Me2PhP)3], and trans-Trichlorobis(dimethylphenylphosphine)(thionitrosyl)rhenium(II), trans-[Re(NS)Cl3(Me2PhP)2], are formed during the reaction of rhenium(V) mixed-ligand complexes of the general formula [ReN(Cl)(Me2PhP)2(R2tcb)] with disulphur dichloride (HR2tcb = N-(N,N-dialkylthiocarbamoyl)benzamidine). The chelating ligands are substituted during the reaction. mer-[Re(NS)Cl2(Me2PhP)3] crystallizes monoclinic in the space group P2(1)/n. The dimensions of the unit cell are a = 8.854(2); b = 31.295(3); c = 11.981(3) angstrom; beta = 108.14(1)degrees; Z = 4. A final R value of 0.033 was achieved on the basis of 5387 reflections with I greater-than-or-equal 3sigma(I). The rhenium atom is coordinated in a distorted octahedral environment. The Me2PhP ligands are arranged meridionally cis to the linear thionitrosyl group. trans-[Re(NS)Cl3(Me2PhP)2] crystallizes in the monoclinic space group C2/c with an unit cell of the dimensions a = 33.320(9); b = 8.446(1); c = 17.281(5) angstrom; 8 = 116.09(1)degrees, Z = 8. The R value converged at 0.026 on the basis of 5 460 independent reflections. The metal is octahedrally coordinated with the phosphine ligands in trans position to each other. The angle Re-N-S is 175.7(3)degrees.