[Ru{sub 3}(CO){sub 9}({mu}{sub 3}-S)]{sup 2{minus}} as a ligand toward [M(CO){sub 3}(NCCH{sub 3})]{sup +}: Synthesis and characterization of HRu{sub 3}(CO){sub 9}({mu}{sub 4}-S)M(CO){sub 3}(NCCH{sub 3}){sub 2} (M = Mn, Re)
- Northwestern Univ., Evanston, IL (United States)
Reactions of the dianionic sulfido cluster [Ru{sub 3}(CO){sub 9}({mu}{sub 3}-S)]{sup 2{minus}} with the lightly stabilized electrophilic cluster-building reagents [M(CO){sub 3}(NCCH{sub 3}){sub 3}]{sup +} (M = Mn, Re) produced the mixed-metal sulfido clusters HRu{sub 3}(CO){sub 9}({mu}{sub 4}-S)Mn-(CO){sub 3}(NCCH{sub 3}){sub 2} and HRu{sub 3}(CO){sub 9}({mu}{sub 4}-S)Re(CO){sub 3}(NCCH{sub 3}){sub 2}, which contain a pseudotetrahedral {mu}{sub 4}-sulfido atom. Analoguos reactions of [Ru{sub 3}(CO){sub 9}({mu}{sub 3}-S)]{sup 2{minus}} with [M(CO){sub 5}]{sup +} (M = Mn, Re) yielded clusters identified as HRu{sub 3}-(CO){sub 9}({mu}{sub 4}-S)Mn(CO){sub 5} and HRu{sub 3}(CO){sub 9}({mu}{sub 4}-S)Re(CO){sub 5} in solution. The clusters HRu{sub 3}(CO){sub 9}({mu}{sub 4}-S)M(CO){sub 3}(NCCH{sub 3}){sub 2} (M = Mn, Re) were characterized by liquid secondary ionization mass spectroscopy, and the structure of HRu{sub 3}(CO){sub 9}({mu}{sub 4}-S)Mn(CO){sub 3}(NCCH{sub 3}){sub 2} was determined by single-crystal X-ray diffraction. These molecules contain the triangular ruthenium metal array capped by an SM(CO){sub 3}(NCCH{sub 3}){sub 2} moiety. The {mu}{sub 4}-sulfido ligand may be viewed as a five-electron donor to the ruthenium triangle and a one electron donor to the pendant metal. The hydrogen atom, located in the X-ray experiment, resides on the ruthenium framework. Crystal data for HRu{sub 3}(CO){sub 9}({mu}{sub 4}-S)Mn(CO){sub 3}(NCCH{sub 3}){sub 2}: monoclinic (P2{sub 1}/c (No. 14)), a = 16.418(4){angstrom}, b = 8.865(1){angstrom}, c = 17.550(4) {angstrom}, {beta} = 96.73(2){degrees}, Z = 4, R (R{sub W}) = 0.038 (0.042).
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- FG02-86ER13640
- OSTI ID:
- 47949
- Journal Information:
- Inorganic Chemistry, Vol. 33, Issue 6; Other Information: PBD: 16 Mar 1994
- Country of Publication:
- United States
- Language:
- English
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