Producción Científica Profesorado

Synthesis of Ir(III) complexes with TpMe2 and acac ligands and their reactivity with electrophiles



Salazar Pereda, Verónica

2015

Synthesis of Ir(III) complexes with TpMe2 and acac ligands and their reactivity with electrophilesJudith P. Morales-Cerón, Verónica Salazar-Pereda, Daniel Mendoza-Espinosa, José G. Alvarado-Rodríguez, Julián Cruz-Borbolla, Noemí Andrade-López and José M. Dalton Trans., 2015,44, 13881-13889DOI: 10.1039/C5DT01937K


Abstract


The reaction of the bis(ethylene) complex [TpMe2Ir(C2H4)2] (1) (TpMe2 = hydrotris(3,5-dimethylpyrazolyl)borate) with an excess of 2,4-pentanedione (acetylacetone, Hacac) at 70 C produced a mixture of the Ir(III) complex [TpMe2Ir(acac)(C2H5)] (6) as a major product (67% yield) and two other side complexes [TpMe2Ir(acac)(H)] (7) and [TpMe2Ir(C9H14O2)] (8) in 20 and 13% yields, respectively. According to the proposed reaction mechanism and DFT calculations, complexes 6 and 7 are generated from an 18e? intermediate [TpMe2Ir(C2H4)(acac)(C2H3)] (5) which undergoes either hydrogen insertion or ?-hydride elimination followed by the subsequent loss of a molecule of ethylene. The lowest yielding complex 8 which features a 2-iridafuran is presumably generated from an unusual thermal coupling between one vinylic and one acac moiety. The availability of the acidic ?-proton of the acac ligand was tested by the treatment of complex 6 with Br2 and Cu(NO3)2 rendering the substitution complexes [Tp3-Br,Me2Ir(3-Br-acac)Br] (9) and [TpMe2Ir(3-NO2-acac)(C2H5)] (10) in good yields. The series of heteroleptic iridium(III) compounds display air and moisture stability and have been characterized by NMR, IR, and elemental analyses, and, in the case of 6, 8 and 9, by single-crystal X-ray diffraction analyses.



Producto de Investigación




Artículos relacionados

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

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

The reaction of [H4Ru4(CO)12] with 1-penten-3-yne: dimerization and trimerization through the triple...

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

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

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

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

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

Mild Oxidation of C?C Bonds of Benzoiridacycles

Reactivity of [Os3(CO)10(NCMe)2] and [Os3(CO)10(?-Cl)(?-AuPPh3)] with 4-mercaptopyridine: X-ray stru...