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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Highly symmetric organic ligand-capped Lindqvist structures derived from 3d-elements
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Highly symmetric organic ligand-capped Lindqvist structures derived from 3d-elements

机译：源自3d元素的高度对称的有机配体封端的Lindqvist结构

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Interaction of M(acac)_2 with Ti(OEt)_4 associated with hydrolysis or thermolysis provides with high yields, through the decomposition of the initially formed M_2Ti_2(acac)_4(OEt) _8, M = Ni (1), Co (2), poorly soluble Lindqvist-type products with the formula M_5TiO(acac)_6(OEt)_6, M = Ni (3), Co (4), Mg (5). The compounds 3-5 are isostructural and display a perfect statistical disorder between the OEt groups and 1/2 of the β-diketonate, acac, ligand. The metal atoms constitute a regular octahedron, centered by the oxo-oxygen atom. There is only one symmetrically independent metal site, which imposes it to contain 1/6 of titanium and 5/6 of the divalent metal atom. The oxygen atoms on the surface of the octahedron are doubly bridging and are located above the twelve edges of the octahedron, as is usual for the Lindqvist-type structures. The coordination of the metal atoms is completed by a single terminal oxygen atom. The complexes 3-5 are volatile with decomposition, releasing only homometallic products into the gas phase in the case of 3 and 4, but with a considerable contribution of molecular evaporation in the case of 5. The intermediates 1 and 2 belong to the tetramolybdate, M_4O _(16), structure type. Highly soluble 1 and 2 can be considered as attractive molecular precursors for the incorporation of 3 and 4 into porous matrices for the preparation of combustion catalysts. Application of the same synthetic approach to n-propoxide complexes offers in a Co-Ti system a derivative with a different composition and resolved metal and ligand disorder, Co_4Ti_2O(acac)_4(O~nPr)_(10) (6), which, however, still follows the Lindquist type and displays high (tetragonal) symmetry for both the molecule and the crystal structure.
机译：通过分解最初形成的M_2Ti_2（acac）_4（OEt）_8，M = Ni（1），Co（2），M（acac）_2与与水解或热解相关的Ti（OEt）_4的相互作用提供了高收率。 ），分子式为M_5TiO（acac）_6（OEt）_6，M = Ni（3），Co（4），Mg（5）的难溶Lindqvist型产品。化合物3-5具有同构结构，并且在OEt基团与β-二酮，acac，配体的1/2之间显示出完美的统计混乱。金属原子构成一个以氧-氧原子为中心的规则八面体。只有一个对称独立的金属位点，使其含有1/6的钛和5/6的二价金属原子。八面体表面的氧原子是双桥联结的，并且位于Lindhvist型结构的通常位置，位于八面体的十二个边缘上方。金属原子的配位通过单个末端氧原子完成。配合物3-5具有分解性的挥发性，在3和4的情况下仅释放均金属产物到气相中，而在5的情况下对分子蒸发有很大贡献。中间体1和2属于四钼酸盐， M_4O _（16），结构类型。高度可溶的1和2可以被认为是将3和4掺入多孔基质中以制备燃烧催化剂的有吸引力的分子前体。将相同的合成方法应用于正丙醇配合物可在Co-Ti系统中提供具有不同组成和可分辨的金属和配体无序的衍生物Co_4Ti_2O（acac）_4（O〜nPr）_（10）（6），但是，仍然遵循Lindquist类型，并且对于分子和晶体结构都显示出高（四边形）对称性。

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