Dancing multiplicity states supported by a carboxylated group in dicopper structures bonded to O2
Dancing multiplicity states supported by a carboxylated group in dicopper structures bonded to O2
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由与 O2 键合的二铜结构中的羧化基团支持的舞蹈多重态
DOI：
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发表时间：
2013
影响因子：
1.7
通讯作者：
L. Cavallo
中科院分区：
文献类型：
--
作者：
A. Poater;L. Cavallo
本研究假定分配正确的多重态双核铜配合物时，与自由分子氧相互作用。最近，通过晶体学表征了通过抗衡离子（允许连接两个金属中心原子的双桥的羧酸酯基团）的直接相互作用稳定的桥蝶μ-η2：η2-过氧双铜核心结构的形成。该系统被指定为双自由基单重态，Ms = 0。然而，经过新的计算，它已被证明是三重态（Ms = 1），尽管后者的多重态的稳定性不高。在这里，有助于使这种结构显示相对于先前预期的双自由基单线态不同的多重性的因素进行了描述。在目前的理论研究中，αSp配体的约束和抗衡的作用被解开。另一方面，还讨论了蝶形μ-η2：η2-过氧结构与同分异构的双（μ-氧代）物种之间的相对稳定性。尽管所有这些结构或电子异构体物质的相对稳定性被认为取决于计算方法，这是难以得出关于活性物质的性质的明确结论的，但在此使用纯或不纯DFT泛函的所有DFT方法得出相同的结论，有利于三重态作为蝴蝶μ-η2的基态：η2-过氧二铜核结构，以及当去除苯甲酸根时的双（μ-氧代）物种。
The present study pretends to assign the correct multiplicity state to dinuclear copper complexes when interacting with free molecular oxygen. Recently, the formation of a bridge butterfly μ–η2:η2-peroxo dicopper core structure stabilized by the direct interaction of the counterion, a carboxylate group that allows the double bridge linking both metal-centre atoms, was characterized by crystallography. This system was assigned as a diradical singlet with Ms = 0. However, after new calculations it has turned out to be triplet (Ms = 1) despite the stabilization for this latter multiplicity state is not high. Here, the factors that contribute to make this structure display a multiplicity different with respect to the previously expected diradical singlet are described. In the present theoretical study, the roles of the αSp ligand constraints and the counterion are unravelled. On the other hand, the relative stability between the butterfly μ–η2:η2-peroxo structure and the isomeric bis(μ-oxo) species is also on discussion. Despite the relative stabilities of all these either structural or electronic isomeric species are supposed to depend on the computational method, which is a difficulty to reach a definite conclusion about the nature of the active species, all DFT methods using either pure or not pure DFT functionals here reach the same conclusion, favoring the triplet as the ground state for the butterfly μ–η2:η2-peroxo dicopper core structure, and the bis(μ-oxo) species when removing the benzoate counterion.
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