NDLI: Synthesis of Ir(III) complexes with $Tp^{Me2}$ and acac ligands and their reactivity with electrophiles

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Cruz-borbolla, Julián Morales-cerón, Judith P. Salazar-pereda, Verónica Alvarado-rodríguez, José G. Mendoza-espinosa, Daniel Vásquez-pérez, José M. Andrade-lópez, Noemí
Description	Author Affiliation: Morales-Cerón JP ( Área Académica de Química, Universidad Autónoma del Estado de Hidalgo, Carretera Pachuca-Tulancingo Km. 4.5, Mineral de la Reforma, Hidalgo, 42090, México. salazar@correo.azc.uam.mx.)
Abstract	The reaction of the bis(ethylene) complex $[Tp^{Me2}Ir(C_{2}H_{4})_{2}]$ (1) $(Tp^{Me2}$ = 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 $[Tp^{Me2}Ir(acac)(C_{2}H_{5})]$ (6) as a major product (67% yield) and two other side complexes $[Tp^{Me2}Ir(acac)(H)]$ (7) and $[Tp^{Me2}Ir(C_{9}H_{14}O_{2})]$ (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 $[Tp^{Me2}Ir(C_{2}H_{4})(acac)(C_{2}H_{3})]$ (5) which undergoes either hydrogen insertion or β-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 α-proton of the acac ligand was tested by the treatment of complex 6 with $Br_{2}$ and $Cu(NO_{3})_{2}$ rendering the substitution complexes $[Tp^{3-Br,Me2}Ir(3-Br-acac)Br]$ (9) and $[Tp^{Me2}Ir(3-NO_{2}-acac)(C_{2}H_{5})]$ (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.
ISSN	14779226
Issue Number	31
Journal	Dalton Trans.
Volume Number	44
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2015-08-21
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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