Producción Científica Profesorado

Reactivity Studies of Iridium Pyridylidenes [TpMe2Ir(C6H5)2(C(CH)3C(R)NH] (R=H, Me, Ph)



Salazar Pereda, Verónica

2013

Cristobal, C; Hernandez, YA; Lopez-Serrano, J ; Paneque, M; Petronilho, A; Poveda, ML; Salazar, V; Vattier, F; Alvarez, E; Maya, C; Carmona, E. ,Reactivity Studies of Iridium Pyridylidenes [TpMe2Ir(C6H5)2(C(CH)3C(R)NH] (R=H, Me, Ph), CHEMISTRY-A EUROPEAN JOURNAL ., Año 2013, Volume: 19 Issue: 12 Pages: 4003-4020 DOI: 10.1002/chem.201203818 ISSN: 0947-6539


Abstract


The reactivity of a series of iridiumpyridylidene complexes with the formula [TpMe2Ir(C6H5)2(C(CH)3C(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 [TpMe2Ir(phenyl)(pyridyl)] intermediates, which behave as internal frustrated Lewis pairs (FLPs). H2 is heterolytically split to give hydridepyridylidene complexes, whilst CO, CO2, and H2CO provide carbonyl, carbonate, and alkoxide species, respectively. Ethylene and propene form five-membered metallacycles with an IrCH2CH(R)N (R=H, Me) motif, whereas, in contrast, acetylene affords four-membered iridacycles with the IrC(CH2)N moiety. C6H5(CO)H and C6H5CCH react with formation of IrC6H5 and IrCCPh 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.



Producto de Investigación




Artículos relacionados

Synthetic, Mechanistic, and Theoretical Studies on the Generation of Iridium Hydride Alkylidene and ...

The reaction of [Ru3(CO)12] with bis(diphenylphosphino)amine. The crystal and molecular structure of...

Reactivity of Triosmium Carbonyl Clusters with 1,8-Diaminonaphthalene ? Synthesis and Structural Cha...

Understanding and Predicting Distorted T- versus Y-Geometries for Neutral Chromous Complexes Support...

CH and CC bond activations of terminal alkynes in the presence of a butterfly-shaped heteronuclear R...

Reactivity of TpMe2Ir(C2H4)(DMAD) with carboxylic acids. A DFT study on geometrical isomers and stru...

Pyrolysis of [Ru3(CO)10(dppe)]: activation of C?H and P?Ph bonds.: The crystal structure and dynamic...

Monodentate, N-Heterocyclic Carbene-Type Coordination of 2,2?-Bipyridine and 1,10-Phenanthroline to ...

Metallacyclic Pyridylidene Structures from Reactions of Terminal Pyridylidenes with Alkenes and Acet...

Synthesis of homo- and heteronuclear rutheniumgold clusters with diphosphine and thiolato bridged li...