Topological analysis of the bonds in incomplete cuboidal [Mo3S4] clusters
Topological analysis of the bonds in incomplete cuboidal [Mo3S4] clusters
复制标题
不完整立方体[Mo3S4]团簇中键的拓扑分析
DOI：
10.1039/b202907c
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发表时间：
2002
影响因子：
3.3
通讯作者：
B. Silvi
中科院分区：
文献类型：
--
作者：
M. Feliz;R. Llusar;J. Andrés;S. Berski;B. Silvi
本文用化学键的拓扑理论研究了[M_3X_13]型三核[Mo_3S_4Cl_3（PH_3）_6]~+簇合物的成键作用。在钼-钼和钼-配体键临界点（bcps）的电子密度的值是小的，使得使用电子密度作为标量函数的键的拓扑描述困难。使用离域指数δ（A，B）或通过电子定域函数（ELF）η（r）的拓扑分析可以更好地理解不同键的特征。涉及[Mo 3S 4]团簇核心内Mo和S中心的离域指数与主要共价键一致
Mo-Mo键和Mo-S键的特征。[Mo 3S 4]单元在第一个ELF分叉图中被明确地确定为一个化学实体，并且进一步增加η（r）值将Mo-S和S价域与[Mo 3]核心的价域分开，[Mo 3]核心进一步分裂为三个双突触V（Mo，Mo）盆地和一个三突触V（Mo，Mo，Mo）盆地。计算结果表明，Mo-（μ ~ 2-S）-Mo键是离域的。对V（Mo，Mo）和V（Mo，Mo，Mo）盆地的轨道贡献的分析使我们能够建立键的拓扑和MO图像之间的关系。
The nature of the bonding interactions within the trinuclear [Mo3S4Cl3(PH3)6]+ cluster with an [M3X13] structural type has been investigated using the present topological theories of the chemical bond. The values of the electron density at the Mo–Mo and Mo–ligand bond critical points (bcps) are small, making a topological description of the bond using the electron density as the scalar function difficult. The characteristics of the different bonds can be better understood using the delocalization index, δ(A, B), or through a topological analysis of the electron localization function (ELF), η(r). The delocalization indexes involving the Mo and S centers within the [Mo3S4] cluster core are in good agreement with the predominant covalent
character of the Mo–Mo and Mo–S bonds. The [Mo3S4] unit is unambiguously identified as a chemical entity in the first ELF bifurcation diagram, and futher increasing the η(r) value separates the the Mo–S and S valence domains from that of the [Mo3] core, which further splits into three disynaptic V(Mo, Mo) basins and one trisynaptic V(Mo, Mo, Mo) basin. Calculations of the basin populations and their covariances suggest the existance of a delocalized Mo-(μ2-S)-Mo bond. Analysis of the orbital contribution to the V(Mo, Mo) and V(Mo, Mo, Mo) basins enables us to establish a relationship between the topological and the MO picture of the bond.
DOI：
10.1002/anie.199420691
发表时间：
1994-11-02
期刊：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH
影响因子：
--
作者：
HAUSSERMANN, U;WENGERT, S;NESPER, R
通讯作者：
NESPER, R