TRANSITION-METAL COMPLEXES WITH SULFUR LIGANDS .82. H2S, S2, AND CS2 MOLECULES AS LIGANDS IN SULFUR-RICH [RU(PPH3)S4] COMPLEXES (S42-= 1,2-BIS[(2-MERCAPTOPHENYL)THIO]ETHANE(2-))

Red [Ru(PPh3)'S4']x ('S4'2 = 1,2-bis[(2-mercaptophenyl)thio]ethane(2-)) reacts in liquid H2S at -70-degrees-C to give [Ru(SH2)(PPh3)'S4'] (1) which recrystallizes from H2S-saturated THF as 1.THF in yellow-orange single crystals. Crystals of 1.THF are monoclinic, space group P2(1)/c, with a = 1124.7 (9) pm, b = 1378.5 (14) pm, c = 2274.0 (16) pm, beta = 97.06 (6)degrees, V = 3499 (5) x 10(6) pm3, Z = 4, and R, (R) = 0.056 (0.065) for 3366 reflections. 1.THF is the first of the rare and often very unstable H2S complexes that could be characterized by X-ray crystallography and shows how H2S in complexes with sulfur-dominated coordination spheres is stabilized by hydrogen bonds. 1 and 1-THF are rapidly oxidized by O2 to yield deep turquoise-blue [(mu-S2){Ru(PPh3)'S4'}2] (2) which has a trans eta-1-eta-1-S2 bridge and exists in two diastereomeric forms as proved by X-ray structure determination of 2-CH2Cl2 and 2.CS2. Crystals of 2-CH2Cl2 are triclinic, space group P1BAR, with a = 999.5 (5) pm, b = 1043.7 (7) pm, c = 1672.4 (14) pm, a = 78.89 (6)-degrees, beta = 89.46 (5)-degrees, gamma = 75.43 (5)-degrees, V = 1655 (2) x 10(6) pm3, and Z = 1. Due to unsatisfactory crystal quality, the structure could not be fully refined. Crystals of 2.CS2 are monoclinic, space group P2(1)/c, with a = 2695.6 (10) pm, b = 1289.9 (4) pm, c = 1947.7 (6) pm, beta = 105.66 (3)-degrees, V = 6519 (4) x 10(6) pm3, Z = 4, and R(w) (R) = 0.068 (0.079) for 7754 reflections. The RuSSRu core in 2 is a chromophore and is described as delocalized 4c-6e pi system. A high degree of sulfur coordination at the Ru centers is assumed to be responsible for the unusual electronic properties of 2 compared with other mu-S2 complexes. Addition of CS2 to [Ru(PPh3)S4'] fragments leads to formation of binuclear deep red [{Ru(PPh3)}(mu-'S4'CS2){Ru(PPh3)'S4'}] (3;'S4'CS22- = 2-[[2-[(2-mercaptophenyl)-thio]ethyl]thio]phenyl trithiocarbonate(2-)) that exists in two diastereomeric pairs of enantiomers. One pair was characterized by X-ray crystallography of 3.CS2 that contains a bridging thioxanthate ligand in an unprecedented bonding mode. Crystals of 3.CS2 are monoclinic, space group P1BAR, with a = 1352.9 (6), b = 1414.9 (10), c = 1848.4 (17) pm, a = 76.79 (6)-degrees, 68.87 (5)-degrees, gamma = 85.93 (5)-degrees, V = 3211 (4) x 10(6) pm3, Z = 2, and R(w) (R) = 0.082 (0.104) for 3954 reflections.