title: Reactivity studies of iridium pyridylidenes [Tp(Me2)Ir(C(6)H(5))(2)(C(CH)(3)C(R)NH] (R=H, Me, Ph).
abstract: The reactivity of a series of iridiumpyridylidene complexes with the formula [Tp(Me2) Ir(C6 H5 )2 (C(CH)3 C(R)NH] (1 a-1 c) towards a variety of substrates, from small molecules, such as H2 , O2 , carbon oxides, and formaldehyde, to alkenes and alkynes, is described. Most of the observed reactivity is best explained by invoking 16 e(-) unsaturated [Tp(Me2) Ir(phenyl)(pyridyl)] intermediates, which behave as internal frustrated Lewis pairs (FLPs). H2 is heterolytically split to give hydridepyridylidene complexes, whilst CO, CO2 , and H2 CO provide carbonyl, carbonate, and alkoxide species, respectively. Ethylene and propene form five-membered metallacycles with an IrCH2 CH(R)N (R=H, Me) motif, whereas, in contrast, acetylene affords four-membered iridacycles with the IrC(CH2 )N moiety. C6 H5 (CO)H and C6 H5 CCH react with formation of IrC6 H5 and IrCCPh bonds and the concomitant elimination of a molecule of pyridine and benzene, respectively. Finally the reactivity of compounds 1 a-1 c against O2 is described. Density functional theory calculations that provide theoretical support for these experimental observations are also reported.
authors: Instituto de Investigaciones Químicas (IIQ) and Departamento de Química Inorgánica, Consejo Superior de Investigaciones Científicas (CSIC) and Universidad de Sevilla, Av. Américo Vespucio 49, Isla de la Cartuja, 41092 Sevilla, Spain.
authors: Crispín
authors: C
authors: Cristóbal
authors: Yohar A
authors: YA
authors: Hernández
authors: Joaquín
authors: J
authors: López-Serrano
authors: Margarita
authors: M
authors: Paneque
authors: Ana
authors: A
authors: Petronilho
authors: Manuel L
authors: ML
authors: Poveda
authors: Verónica
authors: V
authors: Salazar
authors: Florencia
authors: F
authors: Vattier
authors: Eleuterio
authors: E
authors: Álvarez
authors: Celia
authors: C
authors: Maya
authors: Ernesto
authors: E
authors: Carmona