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Structure‐directing sulfur…metal noncovalent semicoordination bonding
Author(s) -
Ananyev Ivan V.,
Bokach Nadezhda A.,
Kukushkin Vadim Yu.
Publication year - 2020
Publication title -
acta crystallographica section b
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.604
H-Index - 33
ISSN - 2052-5206
DOI - 10.1107/s2052520620005685
Subject(s) - natural bond orbital , intramolecular force , chemistry , atoms in molecules , non covalent interactions , crystallography , substituent , chalcogen , metal , atom (system on chip) , molecule , computational chemistry , electron localization function , atomic orbital , transition metal , density functional theory , chemical physics , hydrogen bond , stereochemistry , electron , physics , quantum mechanics , organic chemistry , computer science , embedded system , catalysis
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.

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