TY - JOUR

T1 - Structure-directing sulfur metal noncovalent semicoordination bonding

AU - Ananyev, Ivan V.

AU - Bokach, Nadezhda A.

AU - Kukushkinc, Vadim Yu

N1 - Funding Information: The theoretical part of this work was supported by the Russian Science Foundation (project 18-73-10131 for IVA). VYK is also grateful to the Russian Foundation of Basic Research (project 18-29-04006) for the support of CSD data processing and South Ural State University (Act 211 Government of the Russian Federation, contract No 02.A03.21.0011) for putting facilities at his disposal. Publisher Copyright: © 2020. Copyright: Copyright 2020 Elsevier B.V., All rights reserved.

PY - 2020/6

Y1 - 2020/6

N2 - 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.

AB - 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.

KW - chalcogen bond

KW - charge transfer

KW - CSD

KW - noncovalent interactions

KW - real-space methods

KW - semicoordination

KW - DEFINITION

KW - semi-coordination

KW - CORRELATED MOLECULAR CALCULATIONS

KW - CRYSTAL-STRUCTURE

KW - COMPLEXES

KW - TERMS

KW - COORDINATION

KW - ENERGY DENSITY

KW - ATOMS

KW - GAUSSIAN-BASIS SETS

KW - ELECTRON-DENSITY

UR - http://www.scopus.com/inward/record.url?scp=85090076101&partnerID=8YFLogxK

U2 - 10.1107/S2052520620005685

DO - 10.1107/S2052520620005685

M3 - Article

C2 - 32831262

AN - SCOPUS:85090076101

VL - 76

SP - 436

EP - 449

JO - Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials

JF - Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials

SN - 2052-5192

IS - Pt 3

ER -