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首页> 外文期刊>Chemistry: A European journal >Understanding lead chemistry from topological insights: The transition between holo- and hemidirected structures within the [Pb(CO)(n)](2+) model series
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Understanding lead chemistry from topological insights: The transition between holo- and hemidirected structures within the [Pb(CO)(n)](2+) model series

机译：从拓扑洞察力了解铅化学：[Pb（CO）（n）]（2+）模型系列内全向和半定向结构之间的过渡

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In this Contribution, we focus to the currently unknown [Pb(CO)(n)](2+) model series (n=1 to 10), a set of compounds which allows us to investigate in-depth the holo- and hemidirectional character that lead complexes can exhibit. By means of DFT computations performed using either relativistic four- component formalisms coupled to all-electron basis sets for [Pb(CO)](2+), [Pb(OC)](2+) and [Pb(CO)(2)](2+), or scalar relativistic pseudopotentials for higher n values, the structure and the energetics of these species are investigated. The results are complemented by Constrained Space Orbital Variations (CSOV) and Electron Localization Function (ELF) comprehensive analyses in order to get better insights into the poorly documented chemical fundamentals of the Pb2+ cation. Whereas the discrimination between holo- and hemidirected structures is usually done according to the geometry, we here provide a quantitative indicator grounded on (P)V(Pb), the mean charge density of the valence monosynaptic V(Pb) ELFic basin associated to the metal cation. Free-enthalpy relying discussions show, moreover, that those gas-phase complexes having n = 7, 8 or 9 may be experimentally instable and should dissociate into [Pb(CO)(6)](2+) and a number of CO ligands. According to second-order differences in energy, it is anticipated that the n = 3 or 6 structures should be the most probable structures in the gas phase. Gathering all data from the present theoretical study allows us to propose some concepts that the versatile structural chemistry of Pb2+ complexes could rely on.
机译：在此贡献中，我们集中于当前未知的[Pb（CO）（n）]（2+）模型系列（n = 1至10），这是一组化合物，使我们可以深入研究全向和半向铅配合物可以表现出的特征。通过使用相对论性的四组分形式主义与[Pb（CO）]（2 +），[Pb（OC）]（2+）和[Pb（CO）（2）的全电子基集耦合的DFT计算来进行）]（2+）或更高n值的标量相对论伪势，研究了这些物质的结构和能量。该结果辅以受约束的空间轨道变化（CSOV）和电子定位功能（ELF）的综合分析，以更好地了解Pb2 +阳离子化学基础不完善的情况。尽管通常根据几何结构来区分全向结构和半定向结构，但我们在此提供了一个基于（P）V（Pb）的定量指标，该价是与P和V相关的单价突触V（Pb）ELFic盆地的平均电荷密度。金属阳离子。此外，依赖自由焓的讨论表明，n = 7、8或9的那些气相络合物在实验上可能不稳定，应分解为[Pb（CO）（6）]（2+）和许多CO配体。根据能量的二阶差异，可以预期n = 3或6个结构应该是气相中最可能的结构。收集当前理论研究的所有数据，使我们能够提出一些Pb2 +配合物的通用化学结构所依赖的概念。

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