The abundance and geometric features of nonbonding contacts between metal centers and `soft' sulfur atoms bound to a non‐metal substituent R were analyzed by processing data from the Cambridge Structural Database. The angular arrangement of M, S and R atoms with ∠(R—S…M) down to 150° was a common feature of the late transition metal complexes exhibiting shortened R—S…M contacts. Several model nickel(II), palladium(II), platinum(II) and gold(I) complexes were chosen for a theoretical analysis of R—S…M interactions using the DFT method applied to (equilibrium) isolated systems. A combination of the real‐space approaches, such as Quantum Theory of Atoms in Molecules (QTAIM), noncovalent interaction index (NCI), electron localization function (ELF) and Interacting Quantum Atoms (IQA), and orbital (Natural Bond Orbitals, NBO) methods was used to provide insights into the nature and energetics of R—S…M interactions with respect to the metal atom identity and its coordination environment. The explored features of the R—S…M interactions support the trends observed by inspecting the CSD statistics, and indicate a predominant contribution of semicoordination bonds between nucleophilic sites of the sulfur atom and electrophilic sites of the metal. A contribution of chalcogen bonding (that is formally opposite to semicoordination) was also recognized, although it was significantly smaller in magnitude. The analysis of R—S…M interaction strengths was performed and the structure‐directing role of the intramolecular R—S…M interactions in stabilizing certain conformations of metal complexes was revealed.

中文翻译：

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结构导向的硫...金属非共价半配位键。

通过处理来自剑桥结构数据库的数据，分析了金属中心与键合到非金属取代基R上的“软”硫原子之间的非键接触的丰度和几何特征。M，S和R原子的∠（R -S… M）降低到150°的角度排列是后期过渡金属络合物的缩短R -S… M接触的共同特征。选择了几种模型镍（II），钯（II），铂（II）和金（I）配合物用于R -S… M的理论分析。使用DFT方法的相互作用（应用于平衡的系统）。现实空间方法的组合，例如分子中的原子量子理论（QTAIM），非共价相互作用指数（NCI），电子定位函数（ELF）和相互作用的量子原子（IQA）和轨道（自然键轨道，NBO） ）方法被用来提供关于金属原子身份及其配位环境的R -S… M相互作用的性质和能量学的见解。R — S… M的探索功能相互作用支持通过检查CSD统计数据观察到的趋势，并表明在硫原子的亲核位点和金属的亲电子位点之间半配位键的主要贡献。硫族元素键的作用（在形式上与半配位相反）也得到了认可，尽管其量级明显较小。进行了R -S… M相互作用强度的分析，揭示了分子内R -S… M相互作用在稳定金属配合物某些构象中的结构指导作用。