Coordination d'anions organophosphores: 2eme partie. Perturbations provoquées par les coordinats “halogéno” et “pseudohalogeno” dans des complexes du zinc(II). Étude par spectro |
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| Authors: | Marie-Thérèse Youinou Jacques-Emile Guerchais G Sturtz |
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| Institution: | 1. Laboratoire de Chimie Minérale, Université de Bretagne Occidentale, Avenue Le Gorgeu, 29283 Brest-CédexFrance;2. Laboratoire de Chimie Hétéró-Organique, Université de Bretagne Occidentale, Avenue Le Gorgeu, 29283 Brest-CédexFrance |
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| Abstract: | Infrared and nuclear magnetic resonance spectroscopy data are presented for a series of complexes ZnXL], where L? denotes the {(C2H5O)2POCHCOCH2NR2}? anion with R = CH3 (La?) or C2H5 (Lb?) and X a halogen or pseudohalogen. The infrared data reveal that the splitting of the absorption v(P → O) depends on the nature of X? and is interpreted in terms of a crystal effect. The following order Cl? < NCO? ~ Br? < I? < NCS? < NCSe? is consistent with the ligand size. Nonequivalent protons on a given methylene group and nonequivalent methyl or ethyl groups bonded to nitrogen are detected by NMR spectroscopy of deuterochloroform solutions of these complexes. With La?, the rate of exchange increases in the order NCO?, Cl?, Br?, X? (X? = I?, NCS?, NCSe?). The kinetic parameters for exchange of nonequivalent N(CH3)2 groups were determined. |
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