Hübner Olaf, Himmel Hans-Jörg
Anorganisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany.
Angew Chem Int Ed Engl. 2020 Jul 13;59(29):12206-12212. doi: 10.1002/anie.202004241. Epub 2020 May 18.
Dinuclear compounds of early transition metals with a high metal-metal bond order are of fundamental interest due to their intriguing bonding situation and of practical interest because of their potential involvement in catalytic processes. In this work, two isomers of V H have been generated in solid Ne by the reaction between V and H and detected by infrared spectroscopy: the linear HVVH molecule ( Σ ground state), which is the product of the spin-allowed reaction between V ( Σ ground state) and H , and a lower-energy, folded V (μ-H) isomer ( A ground state) with two bridging hydrogen atoms. Both isomers are characterized by metal-metal bonding with a high bond order; the orbital occupations point to quadruple bonding. Irradiation with ultraviolet light induces the transformation of linear HVVH to folded V (μ-H) , whereas irradiation with visible light initiates the reverse reaction.
具有高金属-金属键级的早期过渡金属双核化合物，因其有趣的键合情况而具有重要的基础研究价值，又因其可能参与催化过程而具有实际应用价值。在这项工作中，通过V与H在固态Ne中的反应生成了VH的两种异构体，并通过红外光谱进行了检测：线性HVVH分子（基态），它是V（基态）与H之间自旋允许反应的产物，以及一种能量较低、具有两个桥连氢原子的折叠式V(μ-H)异构体（基态）。两种异构体均以高键级的金属-金属键为特征；轨道占据情况表明存在四重键。用紫外光照射会促使线性HVVH转变为折叠式V(μ-H)，而用可见光照射则引发逆反应。
