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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Influencing the coordination mode of tbta (tbta = tris[(1-benzyl-1H-1,2,3- triazol-4-yl)methyl]amine) in dicobalt complexes through changes in metal oxidation states
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Influencing the coordination mode of tbta (tbta = tris[(1-benzyl-1H-1,2,3- triazol-4-yl)methyl]amine) in dicobalt complexes through changes in metal oxidation states

机译：通过金属氧化态的变化影响二甲双胍配合物中tbta的配位模式（tbta =三[（1-苄基-1H-1,2,3-三唑-4-基）甲基]胺）

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The complexes [(tbta)Co(μ-CA_(-2H))Co(tbta)(CH _3CN)](BF_4)_21 and [(tbta)Co(μ-OH) _2Co(tbta)](BF_4)_42 (tbta = tris[(1-benzyl-1H-1, 2,3-triazol-4-yl)methyl]amine and CA = chloranilic acid) were synthesized and characterized by X-ray crystallography, SQUID magnetometry and NMR spectroscopy. The reactions to form these complexes deliver 1 as a paramagnetic species containing two high spin Co(ii) centers, and 2 as a diamagnetic compound with two low spin Co(iii) centers. Structural analysis shows that in 1 the capped-octahedral environment around the Co(ii) centers is highly distorted with rather long bonds between the metal and donor atoms. The tbta ligand binds to the Co(ii) centers through the three triazole nitrogen donor atoms in a facial form, with the Co-N(amine) distance of 2.494(2) ? acting as a capping bond to the octahedron. In the crystal an unusual observation of one acetonitrile molecule statistically occupying the coordination sites at both Co(ii) centers is made. 1 displays a series of intermolecular C-H?Cl and π-π interactions leading to extended three-dimensional structures in the solid state. These interactions lead to the formation of voids and explain why only one acetonitrile molecule can be bound to the dinuclear complexes. In contrast to 1, the cobalt centers in 2 display a more regular octahedral environment with shorter cobalt-donor atom distances, as would be expected for a low spin Co(iii) situation. The tbta ligand acts as a perfect tetradentate ligand in this case with the cobalt-N(amine) distance of 2.012(3) ? falling in the range of a normal bond. Thus, we present the rare instances where the ligand tbta has been observed to bind in a perfectly tetradentate fashion in its metal complexes. The room temperature magnetic moment of 6.30 μB for 1 shows values typical of two high spin Co(ii) centers, and this value decreases at temperatures lower than 30 K indicating a weak antiferromagnetic coupling and zero field splitting. Mass spectrometric analysis of 2 provided evidence for the formation of an oxo-bridged dicobalt complex in the gas phase.
机译：[[tbta）Co（μ-CA_（-2H））Co（tbta）（CH _3CN）]（BF_4）_21和[[tbta）Co（μ-OH）_2Co（tbta）]（BF_4）_42（合成了tbta ＝三[[（1-苄基-1H-1，2，3-三唑-4-基）甲基]胺和CA ＝氯苯甲酸），并通过X射线晶体学，SQUID磁力法和NMR光谱表征。形成这些配合物的反应以1为顺磁性物质，包含两个高自旋Co（ii）中心，以2为抗磁性化合物，具有两个低自旋Co（iii）中心。结构分析表明，在1中，Co（ii）中心周围的封端八面体环境高度扭曲，金属与施主原子之间的键较长。 tbta配体通过三个三唑氮供体原子以面部形式与Co（ii）中心结合，Co-N（胺）距离为2.494（2）？。充当八面体的封端键。在晶体中，一个乙腈分子在统计上占据了两个Co（ii）中心的配位点，这是一个不寻常的发现。图1显示了一系列分子间的C-H 2 Cl和π-π相互作用，从而导致固态的扩展三维结构。这些相互作用导致空隙的形成，并解释了为什么只有一个乙腈分子可以与双核复合物结合。与1相反，在2中的钴中心显示出更规则的八面体环境，且钴供体原子距离更短，这在低自旋Co（iii）情况下是可以预期的。在这种情况下，tbta配体充当完美的四齿配体，钴-N（胺）距离为2.012（3）？落在正常键的范围内。因此，我们提出了罕见的例子，其中已经观察到配体tbta在其金属配合物中以完美的四齿形式结合。 1的室温磁矩为6.30μB，显示了两个高自旋Co（ii）中心的典型值，并且该值在温度低于30 K时降低，表明弱的反铁磁耦合和零场分裂。 2的质谱分析提供了在气相中形成氧代桥联的二钴络合物的证据。

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