Computational design of valence tautomeric adducts of Co(II) diketonates with redox-active o-benzoquinone ligands.
Computational design of valence tautomeric adducts of Co(II) diketonates with redox-active o-benzoquinone ligands.
复制标题
Co(II) 二酮酸盐与氧化还原活性邻苯醌配体的价互变异构加合物的计算设计。
作者：
V. Minkin;A. Starikova;R. M. Minyaev
用密度泛函B3 LYP */6-311++G（d，p）方法研究了四配位过渡金属配合物与双齿配体形成稳定加合物的结构设计.对Co（II）二酮与邻苯醌及其单亚胺和二亚胺的一系列加合物进行了计算，结果表明，双-（六氟乙酰丙酮化物）Co（II）与邻苯醌、邻苯醌亚胺和邻苯醌二亚胺的反应满足了表现出VT行为的化合物所要满足的一整套必要条件（加合物相对于分解成组分的稳定性、低自旋电子态的能量偏好和对分子内电子转移的热可实现的能垒决定VT重排的内在机制）。这些化合物可以被认为是一个可行的合成目标的广泛的混合配体VT配合物。
A new concept for the structural design of valence tautomeric (VT) metal complexes involving the formation of stable adducts of a tetracoordinate transition metal complex with a suitable bidentate redox-active ligand has been computationally studied using the DFT B3LYP*/6-311++G(d,p) method. The calculations, performed on a series of adducts of Co(II) diketonates with o-benzoquinone and its mono- and diimines, showed that the mixed-ligand complexes of bis-(hexafluoroacetylacetonate) Co(II) with o-benzoquinone, o-benzoquinone imine and o-benzoquinone diimine satisfy the whole set of necessary conditions to be met by compounds exhibiting VT behaviour (stability of the adduct with respect to dissociation into the components, energy preference of the low-spin electronic state and thermally achievable energy barrier to intramolecular electron transfer determining the intrinsic mechanism of VT rearrangements). These compounds can be regarded as a feasible synthetic target of a broad series of mixed-ligand VT complexes.