THIOLATE-BRIDGED DICHROMIUM COMPLEXES - SYNTHESES AND CRYSTAL-STRUCTURES OF [CPCR(CO)2(SPH)]2 AND [CPCR(SPH)]2S

The predominant product obtained from the reaction of [CpCr(CO)3]2 with Ph2S2 varied with reaction temperature as follows: [CpCr(CO)2(SPh)]2 (3), 32.9%, ambient temperature; [CpCr(CO)(SPh)]2 (4), 53.07%, 60-degrees-C; [CpCr(SPh)]2S (5), 20.7%, 80-degrees-C. A thermolysis study showed the degradation of 3 and 4 to 5 and eventually to Cp4Cr4S4. The thiolate-bridged complexes have been characterized by elemental and spectral analyses. 3 and 5 have also been structurally determined. Crystal data: 3, monoclinic, space group P2(1)/c (No. 14), a = 9.138 (2) angstrom, b = 14.195 (6) angstrom, c = 18.879 (5) angstrom, beta = 101.77 (2)-degrees, V = 2397 (1) angstrom 3, Z = 4; 5, triclinic, space group P1BAR (No. 2), a = 9.548 (1) angstrom, b = 10.122 (2) angstrom, c = 13.003 (1) angstrom, alpha = 103.71 (1)-degrees, beta = 100.351 (9)-degrees, gamma = 98.62 (1)-degrees, V = 1176.4 (3) angstrom 3, Z = 1.