Synthesis, Structural Characterization, Reactivity, and Catalytic Properties of Copper(I) Complexes with a Series of Tetradentate Tripodal Tris(pyrazolylmethyl)amine Ligands
Article
文ちゃんのコンペティターのところの論文。いつもと少し趣向の違う結晶構造に関する論文ですが、後ろの方で、PhINTsをつかったアルケンの酸化してます。この配位子をつかって過酸化水素の系もおそらくそのうち出てきます。
Estela Haldón †, Manuela Delgado-Rebollo †,Auxiliadora Prieto ‡, Eleuterio Álvarez §, Celia Maya§, M. Carmen Nicasio *
, and Pedro J. Pérez *†
, and Pedro J. Pérez *†
† Laboratorio de Catálisis Homogénea, Unidad Asociada al CSIC, CIQSO-Centro de Investigación en Química Sostenible and Departamento de Química y Ciencias de los Materiales, Universidad de Huelva, Campus de El Carmen s/n, 21007 Huelva, Spain
‡ Laboratorio de Catálisis Homogénea, Unidad Asociada al CSIC, CIQSO-Centro de Investigación en Química Sostenible and Departamento de Ingeniería Química, Química Física y Química Orgánica, Universidad de Huelva, Campus de El Carmen s/n, 21007 Huelva, Spain
§ Instituto de Investigaciones Químicas Isla de la Cartuja, CSIC-Universidad de Sevilla, Avenida de Américo Vespucio 49, 41092 Sevilla, Spain
Departamento de Química Inorgánica, Universidad de Sevilla, Apartado 1203, 41071 Sevilla, Spain
Inorg. Chem., Article ASAP
DOI: 10.1021/ic500311y
Publication Date (Web): April 3, 2014
Copyright © 2014 American Chemical Society
*E-mail: mnicasio@us.es., *E-mail: perez@dqcm.uhu.es.
Abstract
Novel tris(pyrazolylmethyl)amine ligands TpaMe3, Tpa*,Br, and TpaBr3 have been synthesized and structurally characterized. The coordination chemistries of these three new tetradentate tripodal ligands and the already known Tpa and Tpa* have been explored using different copper(I) salts as starting materials. Cationic copper(I) complexes [TpaxCu]PF6 (1–4) have been isolated from the reaction of [Cu(NCMe)4]PF6 and 1 equiv of the ligand. Complexes 2(Tpax = Tpa*) and 3 (Tpax = TpaMe3) have been characterized by X-ray studies. The former is a 1D helical coordination polymer, and the latter is a tetranuclear helicate. In both structures, the Tpax ligand adopts a μ2:κ2:κ1-coordination mode. However, in solution, all of the four complexes form fluxional species. When CuI is used as the copper(I) source, neutral compounds 5–8 have been obtained. Complexes 6–8 exhibit a 1:1 metal-to-ligand ratio, whereas 5 presents 2:1 stoichiometry. Its solid-state structure has been determined by X-ray diffraction, revealing its 3D polymeric nature. The polymer is composed by the assembly of [Tpa2Cu4I4] units, in which Cu4I4 presents a step-stair structure. The Tpa ligands bridge the Cu4I4 clusters, adopting also a μ2:κ2:κ1-coordination mode. As observed for the cationic derivatives, the NMR spectra of 5–8 show the equivalence of the three pyrazolyl arms of the ligands in these complexes. The reactivities of cationic copper(I) derivatives 1–4 with PPh3and CO have been explored. In all cases, 1:1 adducts [TpaxCuL]PF6 [L = PPh3 (9–11), CO (12–15)] have been isolated. The crystal structure of [Tpa*Cu(PPh3)]PF6 (9) has been obtained, showing that the coordination geometry around copper(I) is trigonal-pyramidal with the apical position occupied by the tertiary amine N atom. The Tpa* ligand binds the Cu center to three of its four N atoms, with one pyrazolyl arm remaining uncoordinated. In solution, the carbonyl adducts 13–15 exist as a mixture of two isomers; the four- and five-coordinate species can be distinguished by means of their IR νCO stretching bands. Finally, the catalytic activities of complexes 1–4 have been demonstrated in carbene- and nitrene-transfer reactions.
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