Chemistry of [Cp[sup *]Rh([mu]-Cl)][sub 2] and its dioxygen and nitrosobenzene insertion products

Journal Article · Wed Mar 03 04:00:00 EST 1993 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00057a021· OSTI ID:7069948

Hoard, D W; Sharp, P R ^[1]

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1. 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), Journal Name: Inorganic Chemistry; (United States) Vol. 32:5; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
AROMATICS
CHEMICAL REACTIONS
CHLORIDES
CHLORINE COMPOUNDS
CRYSTAL STRUCTURE
ELEMENTS
HALIDES
HALOGEN COMPOUNDS
MAGNETIC RESONANCE
NITROSO COMPOUNDS
NONMETALS
NUCLEAR MAGNETIC RESONANCE
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXYGEN
REFRACTORY METAL COMPOUNDS
RESONANCE
RHODIUM COMPOUNDS
TRANSITION ELEMENT COMPOUNDS