A trichloro-bridged diruthenium(II,III) complex: Preparation, properties and X-ray structure of tri(-{mu}-chloro)dichlorocarbonyltris (triphenylphosphine)diruthenium(II,III)
- Universidade Federal de Sao Carlos (Brazil)
- Universidade de Sao Paulo, Sao Carlos (Brazil)
The triply chloro-bridged binuclear complex [Ru{sub 2}Cl{sub 5}(CO)(PPh{sub 3}){sub 3}]{center_dot}CH{sub 2}Cl{sub 2}, (PPh{sub 3} = triphenylphosphine), M{sub r} = 1279.23, prepared from the precursor compound [RuCl{sub 3}(PPh{sub 3}){sub 2}DMA]{center_dot}DMA (DMA = N, N{prime}-dimethylacetamide) and crystallizes in the monoclinic space group P2{sub 1/3}. The structure was solved from 6994 independent reflections for which I > 3{sigma}(I) by Patterson and difference Fourier techniques and refined to a final R = 0.042. The complex is formed by two Ru atoms bridged through three chloride anions. One Ru atom is further coordinated to two non-bridging Cl atoms and a triphenylphosphine ligand, whereas the other is bonded to two PPh{sub 3} ligands and a carbon monoxide molecule. The presence of Ru{sup III} was confirmed by EPR data. The absence of an intervalence charge-transfer transition (IT) in the near-infrared spectrum suggests that the binuclear complex is of a localized valence type. The IR spectrum shows a v{sub CO} band at 1964 cm{sup {minus}1} and v{sub Ru-Cl} bands at 328, 280 cm{sup {minus}1}, corresponding to chlorides at terminal positions and 250, 225 cm{sup {minus}1} for the bridged ones. Two redox processes, Ru{sup II}/Ru{sup II} (E{sub 1/2} = {minus}0.29 V) {l_arrow} Ru{sup II}/Ru{sup III} {yields} (E{sub 1/2} = 1.19 V) Ru{sup III}/Ru{sup III}, were observed by cyclic voltammetry. 32 refs., 4 figs., 3 tabs.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 75725
- Journal Information:
- Journal of Coordination Chemistry, Vol. 30, Issue 3-4; Other Information: PBD: 1993
- Country of Publication:
- United States
- Language:
- English
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