A controlled substitution reaction of [ReOCl3(PPh3)2] with DMT (DMT=2.6-dimethylbenzenethiolate) was achieved using Me3SiDMT to give [ReO(DMT)3(PPh3)] (I). The same complex was obtained from [ReH7(PPh3)2] and the disulfide of DMT, but [Re(DMT)3(PPh3)(PHPh2)] (IV) was isolated from the reaction of [ReH7(PPh3)2] with HDMT. X-ray diffraction studies show that both compounds have a distorted trigonal bipyramidal geometry. Crystal data: I: C42H42OPS3Re, Mr=876.1, monoclinic, space group P21/n, a=11.842(6), b=19.164(8), c=17.368(7) Å, β=104.01(4)°, V=3824(3)Å3, Z=4, R=0.342 (Rw=0.394) for 4156 unique data having F> 5σ(F); IV: C54H53P2ReS3, Mr=1045, monoclinic, space group P21/n, a=11.014(4), b=23.064(4), c=19.017(5) Å, β=97.00(2)°, V=4795(2) Å3, Z=4, R=0.060, Rw=0.084, for 4705 independent observed reflections having F> 3σ(F). © 1994.
