Transition-metal complexes with sulfur ligands. 82. H{sub 2}S, S{sub 2}, and CS{sub 2} molecules as ligands in sulfur-rich [Ru(PPh{sub 3})`S{sub 4}] complexes (`S{sub 4}{sup 2-} = 1,2-Bis[(2-mercaptophenyl)thio]ethane(2-))
- Institut fuer Anorganische Chemie der Universitaet Erlangen-Nuernberg, Erlangen (Germany)
Red (Ru(PPh{sub 3}){open_quote}S{sub 4}{close_quote}){sub x} ({open_quote}S{sub 4}{close_quote}{sup 2} = 1,2-bis((2-mercaptophenyl)thio)ethane(2-) reacts in liquid H{sub 2}S at -70 C to give (Ru(SH{sub 2})(PPh{sub 3}){open_quote}S{sub 4}{close_quote}) (1) which recrystallizes from H{sub 2}S-saturated THF as 1-THF in yellow-orange single crystals. 1-THF is the first of the rare and often very unstable H{sub 2}S complexes that could be characterized by X-ray crystallography and shows how H{sub 2}S in complexes with sulfur-dominated coordination spheres is stabilized by hydrogen bonds. 1 and 1-THF are rapidly oxidized by O{sub 2} to yield deep turquoise-blue (({mu}-S{sub 2})(Ru(PPh{sub 3}{open_quote}S{sub 4}{close_quote}){sub 2}) (2) which has a trans {eta}{sup 1}-{eta}{sup 1}-S{sub 2} bridge and exists in two diastereomeric forms as proved by X-ray structure determination of 2{center_dot}CH{sub 2}Cl{sub 2} and 2{center_dot}CS{sub 2}. Crystals of 2{center_dot}CH{sub 2}Cl{sub 2} are triclinic. 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}-S{sub 2} complexes. Addition of CS{sub 2} to (Ru(PPh{sub 3}) {open_quote}S{sub 4}{close_quote}) fragments leads to formation of binuclear deep red ((Ru(PPh{sub 3}))({mu}-{open_quote}S{sub 4}{close_quote}CS{sub 2})(Ru(PPh{sub 3}){open_quote}S{sub 4}{close_quote})) (3; {open_quote}S{sub 4}{close_quote}CS{sub 2}{sup 2{minus}} = 2-))2-((2-mercaptophenyl)-thio)phenyl trithiocarbonate (2-)) that exists in two diastereomeric pairs of enantiomers. One pair was characterized by X-ray crystallography of 3{center_dot}CS{sub 2} that contains a bridging thioxanthate ligand in an unprecedented bonding mode. Crystals of 3{center_dot}CS{sub 2} are monoclinic, space group P1.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 171649
- Journal Information:
- Journal of the American Chemical Society, Vol. 114, Issue 3; Other Information: PBD: 29 Jan 1992
- Country of Publication:
- United States
- Language:
- English
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