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首页> 外文期刊>European journal of inorganic chemistry >Dinuclear Molybdenum(III) and Tungsten(III) Calix[4]arene Complexes - Metal-Metal Triple Bonds Supported by Bridging Calix[4]arene Ligands
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Dinuclear Molybdenum(III) and Tungsten(III) Calix[4]arene Complexes - Metal-Metal Triple Bonds Supported by Bridging Calix[4]arene Ligands

机译：双核钼（III）和钨（III）杯[4]芳烃配合物-杯[4]芳烃配体支持的金属-金属三键

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摘要

Addition of p-tert-butylcalix[4]arene LH_4 to the dinuclear compounds M_2(NMe_2)_6 (M = Mo, W) results in the formation of [NH_2Me_2]_2[L_2M_2] 1 (M = Mo) and 2 (M = W). Both compounds have been characterized by spectroscopic methods and single-crystal X-ray diffraction. The metal-metal distances of 1 and 2, of 2.194(1) A and 2.293(1) A, respectively, are consistent with the retention of the M≡M triple bond. Both "ate" complexes contain a [M≡M]~(6+) dimetal core, supported by two bridging μ_2-κ~2O, κ~2O-calix[4]arene ligands in the solid state. These compounds are the first examples of a formally fourfold deprotonated calix[4]arene acting as a μ_2-κ~2O, κ~2O bridging ligand for two transition metal centres. The calix[4] arenes in 1 and 2 are distorted from a cone conformation in the uncomplexed ligand, to an elliptical cone section. ~1H-NMR data at variable temperatures suggest fluxional behaviour of 1 and 2 in solution.
机译：在双核化合物M_2（NMe_2）_6（M = Mo，W）中加入对叔丁基杯[4]芳烃LH_4导致[NH_2Me_2] _2 [L_2M_2] 1（M = Mo）和2（M = W）。两种化合物均已通过光谱法和单晶X射线衍射进行了表征。 1和2的金属-金属距离分别为2.194（1）A和2.293（1）A，与M≡M三键的保留一致。两种“酸酯”配合物均包含[M≡M]〜（6+）双金属核，并由固态的两个桥接μ_2-κ〜2O，κ〜2O-calix [4]芳烃配体支撑。这些化合物是形式上四重去质子化的杯[4]芳烃的第一个实例，其充当两个过渡金属中心的μ_2-κ〜2O，κ〜2O桥联配体。 1和2中的杯[4]芳烃从非复杂配体的圆锥构象变形为椭圆圆锥部分。可变温度下的1H-NMR数据表明溶液中1和2的通量行为。

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