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首页> 外文期刊>Acta crystallographica. Section C, Structural chemistry. >A tale of hydrogen abstraction, initially detected via X-ray diffraction
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A tale of hydrogen abstraction, initially detected via X-ray diffraction

机译：最初是通过X射线衍射检测到的氢提取物的故事

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摘要

Reaction of a bis-tetrazinyl pyridine pincer ligand, btzp, with a vanadium(III) reagent gives not a simple adduct but dichlorido{3-methyl-6-[6-(6-methyl-1,2,4,5-tetrazin-3-yl-κN2)pyridin-2-yl-κN]-1,4-dihydro-1,2,4,5-tetrazin-1-yl-κN1}oxidovanadium(IV) acetonitrile 2.5-solvate, [V(C11H10N9)Cl2O]·2.5CH3CN, a species which X-ray diffraction reveals to have one H atom added to one of the two tetrazinyl rings. This H atom was first revealed by a short intermolecular N...Cl contact in the unit cell and subsequently established, from difference maps, to be associated with a hydrogen bond. One chloride ligand has also been replaced by an oxide ligand in this synthetic reaction. This formula for the complex, [V(Hbtzp)Cl2O], leaves open the question of both ligand oxidation state and spin state. A computational study of all isomeric locations of the H atom shows the similarity of their energies, which is subject to perturbation by intermolecular hydrogen bonding found in X-ray work on the solid state. These density functional calculations reveal that the isomer with the H atom located as found in the solid state contains a neutral radical Hbtzp ligand and tetravalent d1 V center, but that these two unpaired electrons are more stable as an open-shell singlet and hence antiferromagnetically coupled.
机译：双四嗪基吡啶钳形配体btzp与钒（III）试剂的反应不是简单的加合物，而是二氯基{3-甲基-6- [6-（6-甲基-1,2,4,5-四嗪） -3-yl-κN2）吡啶-2-yl-κN] -1,4-二氢-1,2,4,5-四嗪-1-基-κN1}氧化钒（IV）乙腈2.5-溶剂化物，[V（ C 11 H 10 N 9）Cl 2 O]·2.5CH 3 CN，一种经X射线衍射显示在两个四嗪基环之一上加有一个H原子的物质。该H原子首先通过晶胞中的短分子间N ... Cl接触而暴露出来，然后根据差异图确定与氢键相关。在该合成反应中，一种氯化物配体也已被氧化物配体代替。该络合物[V（Hbtzp）Cl2O]的公式未解决配体氧化态和自旋态的问题。对H原子所有异构位置的计算研究表明，它们的能量相似，这在固态X射线工作中受到分子间氢键的干扰。这些密度泛函计算表明，处于固态的H原子异构体包含一个中性自由基Hbtzp配体和四价d1 V中心，但是这两个未成对的电子作为开壳单线态更稳定，因此反铁磁耦合。

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