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Reactivity of TpIr(C2H4)(DMAD) with carboxylic acids. A DFT study on geometrical isomers and structural characterization |
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| Authors: | Verónica Salazar Gloria Sánchez-Cabrera Julián Cruz Martín Hernández Celia Maya María J Rosales-Hoz |
| Institution: | a Centro de Investigaciones Químicas, Universidad Autónoma del Estado de Hidalgo, Ciudad Universitaria, Km 4.5 Carretera Pachuca-Tulancingo, 42184 Pachuca, Hidalgo, México b Instituto de Investigaciones Químicas, Departamento de Química Inorgánica, Consejo Superior de Investigaciones Científicas (CSIC) and Universidad de Sevilla, Avenida Américo Vespucio 49, Isla de la Cartuja, 41092 Sevilla, Spain c Departamento de Química, Centro de Investigación y de Estudios Avanzados del I.P.N., Avenida Instituto Politécnico Nacional 2508, Col San Pedro Zacatenco, 07360 México D. F., México d Facultad de Química, Universidad Nacional Autónoma de México (UNAM), Ciudad Universitaria, Coyoacán, 04510, México D.F., México |
| Abstract: | The thermally unstable adduct TpMe2Ir(C2H4)(DMAD), which was generated “in situ” by the reaction of DMAD with TpMe2Ir(C2H4)2 (1) at low temperature, reacted with different carboxylic acids to produce the following compounds: TpMe2Ir(E-C(CO2Me) CH(CO2Me))(H2O)(OC(O)C6H4R), (R = H, 2a; o-OH, 2b; o-Cl, 2c; m-Cl, 2d; o-NO2, 2e; m-NO2, 2f;o-Me, 2g;p-Me, 2h) and TpMe2Ir(E-C(CO2Me)CH(CO2Me))(H2O)(OC(O)Me) 3. In the reaction of derivative 2a with Lewis bases, TpMe2Ir(E-C(CO2Me)CH(CO2Me))(L)(OC(O)C6H5), (L = Py, 4a; m-Br-Py, 4b; m-Cl-Py, 4c; NCMe, 5) were obtained, of which 4b and 4c were isolated as a mixture of two isomers in which the substituted pyridine ring was present at different rotational orientations. All new compounds prepared were characterized by 1H and 13C{1H} NMR spectroscopy, the structure of compounds 2d, 2h and 4a being determined by X-ray diffraction analysis. DFT was used to analyze the relative stability and the structural orientation of the isomers. |
| Keywords: | Alkyne insertion TpMe2 iridium complexes Dimethylacetylene dicarboxylate C-H activation DFT calculations |
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