PREPARATION AND CHARACTERIZATION OF DIRHENIUM COMPLEX ANIONS OF THE TYPE [RE2CL7(DITHIOETHER)](-) WITH RE-RE QUADRUPLE BONDS

Two dirhenate(III) anions containing dithioether ligands and Re-Re qua druple bonds have been synthesized and characterized by X-ray crystall ography. Under mild reaction conditions, both 3,6-dithiaoctane (CH3CH2 SCH2CH2SCH2CH3 or dto) and 2,5-dithiahexane (CH3SCH2CH2SCH3 or dth) di splace a single chloride ligand from [Re2Cl8](2-) to yield [Re2Cl7(dto )](-) and [Re2Cl7(dth)](-), respectively. The tetra-n-butylammonium (B u(4)N) salts of these complex ions have been isolated and found to rea ct with additional dithioether to produce the unsymmetrical compounds Re2Cl8(dto)(2) and Re2Cl5(dth)(2) with Re-Re triple bonds. The complex (Bu(4)N)[Re2Cl7(dto)] crystallizes in the triclinic space group <P(1) over bar> with a = 11.299(3), b = 11.552(4), c = 14.654(4) Angstrom, a lpha = 108.19(2), beta = 104.07(2), gamma = 88.65(3)degrees and Z = 2, while (Bu(4)N)[Re2Cl7(dth)] crystallizes in the monoclinic space grou p P2(1) with a = 10.361(2), b = 15.567(4), c = 11.663(3) Angstrom, bet a = 117.01(2)degrees and Z = 2. The Re-Re bond distances are 2.248(1) and 2.257(1) Angstrom for the dto and dth complexes, respectively.