Soluble Ni alkoxides based on dimethylaminoisopropoxide ligands: molecular structure of [Li(PrOH)Ni (η-OR)2Cl]2 and of cis-NiCl2(ROH)2 (R = CHMeCH2NMe2) |
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Authors: | Liliane G. Hubert-Pfalzgraf Vadim G. Kessler Jacqueline Vaissermann |
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Affiliation: | aLaboratoire de Chimie Moléculaire, URA-CNRS, Université de Nice-Sophia-Antipolis, Parc Valrose, 06 108 Nice Cédex 2, France;bLaboratoire de Chimie de Métaux de Transition, URA-CNRS, 4 Place Jussieu, 75 230 Paris Cédex 5, France |
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Abstract: | Various routes to NiII aminoalkoxides have been investigated. A nickel isopropoxide derivative 1 was prepared by anodic dissolution of the metal in the presence of LiCl as electrolyte. Alcoholysis reactions of 1 with 1-dimethylamino-2-propanol afforded the homoleptic nickel(II) aminoalkoxide 2 together with a NiLi species 3. 2 was also obtained by metathesis reactions between sodium alkoxide and the nickel hexammine complex whereas the reaction between the latter and the aminoalcohol led to an halide solvate, cis-NiCl2(η2-ROH)2, 4. The various compounds were characterized by elemental analysis, FT-IR and UV-vis spectroscopies as well as by X-ray diffraction for 3 and 4. 3 corresponds to [Li(PriOH)Ni(η2-OCHMeCH2NMe2)Cl]2 and the overall structure can be seen as two [Ni(η2-OCHMeCH2NMe2)2Cl]− moieties assembled by Li(PriOH)+. The lithium atom is 4-coordinate due to its interaction with the oxygen atoms of the aminoalkoxide ligands. Nickel is 5-coordinate with a distorted tetragonal pyramidal stereochemistry, one nitrogen being in the apical position. The metal displays a distorted octahedral surrounding for the NiCl2 adduct 4. The bond distances vary in the order NiOR < NiN ≈ NiO(H)R < NiCl for 3 and 4. The various compounds (except 1) are soluble in organic media. |
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Keywords: | nickel alkoxides electrosynthesis lithium mixed-metal alkoxides |
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