Chemistry of [Cp[sup *]Rh([mu]-Cl)][sub 2] and its dioxygen and nitrosobenzene insertion products
- Univ. of Missouri, Columbia (United States)
Treating [Cp[sup *]Rh([mu]-Cl)Cl][sub 2] (Cp[sup *] = C[sub 5]Me[sub 5] = pentamethylcyclopentadienyl) with excess Na(Hg) (0.4%) in CH[sub 2]Cl[sub 2] gives deep blue [Cp[sup *]Rh([mu]-Cl)][sub 2] (1). The structure consists of two independent, nearly identical molecules (one on a 2-fold axis and the other in a general position) with short Rh-Rh bonds (2.623 [Angstrom] average), bridging chlorides, and [eta][sup 5]-Cp[sup *] ligands. Methylene chloride solutions of 1 react rapidly with dioxygen at temperatures slightly above [minus]78[degrees]C to give an unstable (above ca. [minus]15[degrees]C in CD[sub 2]Cl[sub 2]) unsymmetrical, dioxygen adduct [(Cp[sup *]Rh)[sub 2]([mu]-Cl)(Cl)([mu],[eta][sup 1]:[eta][sup 2]-O[sub 2])] (2). Complex 2 is fluxional on the NMR time scale. The addition of PPh[sub 3] to cold solutions of 2 gives Cp[sup *]RhCl[sub 2](PPh[sub 3]) and the unstable (above ca. 0[degree]C in CD[sub 2]Cl[sub 2]) complex Cp[sup *]Rh(O[sub 2])(PPh[sub 3]) (3). With excess PMe[sub 3], 2 gives the fulvene complex [([eta][sup 4]-C[sub 5]Me[sub 4]CH[sub 2])Rh(PMe[sub 3])[sub 3]]Cl (4). Treating 1 with PhNO at 22[degrees]C gives [(Cp[sup *]Rh)[sub 2]([mu]-Cl)(Cl)([mu],[eta][sup 1]:[eta][sup 2]-PhNO)] (5) which, by NMR and a crystal structure determination, has a structure similar to that proposed for 2. The structure consists of an [eta][sup 1]:[eta][sup 2]-bound PhNO ligand (bridging the two [eta][sup 5]-Cp[sup *]Rh centers via the nitrogen atom), a bridging Cl, and a terminal Cl bound to the [eta][sup 1]-Rh center. 34 refs., 4 figs., 10 tabs.
- DOE Contract Number:
- FG02-88ER13880
- OSTI ID:
- 7069948
- Journal Information:
- Inorganic Chemistry; (United States), Vol. 32:5; ISSN 0020-1669
- Country of Publication:
- United States
- Language:
- English
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400201* - Chemical & Physicochemical Properties