Mixed ruthenium-rhodium carbonyl clusters. Synthesis and crystal structure of the [PPh{sub 4}]{sup +} salts of the anions [Ru{sub 2}Rh{sub 2}(CO){sub 7}({mu}-CO){sub 5}]{sup 2{minus}}, [Ru{sub 2}Rh{sub 2}(CO){sub 9}({mu}-H)]{sup {minus}}, and [Ru{sub 2}Rh{sub 2}(CO){sub 7}({mu}-CO){sub 5}({mu}{sub 3}-AuPPh{sub 3})]{sup {minus}}
- Universita di Milano (Italy); and others
The anion [Ru{sub 2}Rh{sub 2}(CO){sub 12}]{sup 2{minus}} (1) has been obtained by reaction of Ru{sub 3}(CO){sub 12} with [Rh(CO){sub 4}]{sup {minus}} as [N(PPh{sub 3}){sub 2}]{sup +} or (PPH{sub 4}){sup +} salts; this species reacts with acids or AuPPH{sub 3}Cl to give respectively [Ru{sub 2}Rh{sub 2}(CO){sub 12}H]{sup {minus}} (2) and [Ru{sub 2}Rh{sub 2}(CO){sub 12} (AuPPh{sub 3})]{sup {minus}} (3). The phosphonium salts (PPh{sub 4}){sub 2}[Ru{sub 2}Rh{sub 2}(CO){sub 12}]{center_dot}THF (I), (PPh{sub 4})[Ru{sub 2}Rh{sub 2}(CO){sub 12}H] (II), and (PPh{sub 4})[Ru{sub 2}Rh{sub 2}(CO){sub 12}(AuPPh{sub 3})](III) were characterized by single crystal X-ray diffraction. Anions 1 and 2 have a tetrahedral Ru{sub 2}Rh{sub 2} metal frame, while in 3 there is a trigonal-bipyramidal frame with one ruthenium atom and the gold atom in apical positions; in 2 the H atom bridges the Ru-Ru edge. {sup 1}H and {sup 31}P NMR spectra of, respectively, 2 and 3 are consistent with the crystal structures. {sup 13}C NMR spectra of both 1 and 2 show evidence of fluxional behavior at 295 K which cannot be frozen at 178 K, where the signals collapse; compound 3 at room temperature shows a partially fluxional solution structure which becomes static at ca. 250 K.
- OSTI ID:
- 263744
- Journal Information:
- Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 7 Vol. 35; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
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