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

Mendoza Espinosa, Daniel


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


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.

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