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Reactivity of the terminal oxo species (((t)Bu2PCH2SiMe2)2N)RhO.
Tsvetkov, Nikolay P; Andino, José G; Fan, Hongjun; Verat, Alexander Y; Caulton, Kenneth G.
Afiliación
  • Tsvetkov NP; Indiana University, Department of Chemistry, 800 East Kirkwood Avenue, Bloomington, Indiana, USA.
Dalton Trans ; 42(19): 6745-55, 2013 May 21.
Article en En | MEDLINE | ID: mdl-23571602
ABSTRACT
Reactivity of the 4-coordinate molecule (PNP)RhO (PNP is ((t)Bu2PCH2SiMe2)2N) towards CO proceeds stepwise, first forming an η(2)-CO2 complex, by a mechanism which involves a preliminary adduct of CO on Rh, then a second CO displaces CO2. Reaction of the oxo complex with CO2 occurs in time of mixing even at low temperature to form (PNP)Rh(η(2)-CO3), with no intermediate detectable. DFT calculations indicate an initial bond formation between the oxo center and the CO2 carbon. Reaction of (PNP)RhO with H2 occurs only at a 1 2 molar stoichiometry, to ultimately form (PNP)Rh(H)2 and free H2O. No intermediate reaches detectable population even at -60 °C, but DFT mapping of various possible mechanisms on the singlet energy surface shows that the nearly equi-energetic (PNP)Rh(H2O) and (PNP)RhH(OH) are formed, but only the latter readily adds the second molecule of H2 to proceed to the observed products; these reactions thus both involve heterolytic splitting of H2.

Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Dalton Trans Asunto de la revista: QUIMICA Año: 2013 Tipo del documento: Article País de afiliación: Estados Unidos

Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Dalton Trans Asunto de la revista: QUIMICA Año: 2013 Tipo del documento: Article País de afiliación: Estados Unidos