TY - JOUR

T1 - Metal-Involving Halogen Bonding Including Gold(I) as a Nucleophilic Partner. the Case of Isomorphic Dichloroaurate(I)·Halomethane Cocrystals

AU - Aliyarova, Irina S

AU - Tupikina, Elena Yu

AU - Ivanov, Daniil M.

AU - Kukushkin, Vadim Yu

N1 - Publisher Copyright: © 2022 American Chemical Society.

PY - 2022/2/7

Y1 - 2022/2/7

N2 - Three isomorphic cocrystals were obtained via the crystallization of [PPN][AuCl2] (1) from CHBr3 (1·CHBr3), or CHCl3/1,2-C2F4Br2 (1·CHCl3) and CH2Cl2/Et2O (1·CH2Cl2) mixtures. Analysis of the single-crystal X-ray diffraction data for these cocrystals revealed a gold(I)-involving two-center C-X···Au halogen bond (abbreviated as XB; X = Cl, Br) and a three-center bifurcated C-Br···(Cl-Au) XB; in the latter, the gold(I)-chloride linkage functions as an integrated XB acceptor. The noncovalent nature and energies [spanning from -1.58 to -5.52 kcal/mol for C-X···Au and -6.37 kcal/mol for C-Br···(Cl-Au) XBs] of these noncovalent interactions were studied by density functional theory calculations and topological analysis of the electron density distribution in the framework of the quantum theory of atoms-in-molecules (QTAIM) followed by noncovalent interaction (NCI) analysis at the B3LYP-D3/jorge-TZP-DKH level of theory. The nucleophilicity of the gold(I) centers toward halogens of halomethanes was verified by a set of independent methods including electrostatic potential surfaces, electron localization function projection, natural bond orbital charge transfer, electron density/electrostatic potential profile, Wiberg bond indexes, natural population analysis, and atoms-in-molecules charge analyses.

AB - Three isomorphic cocrystals were obtained via the crystallization of [PPN][AuCl2] (1) from CHBr3 (1·CHBr3), or CHCl3/1,2-C2F4Br2 (1·CHCl3) and CH2Cl2/Et2O (1·CH2Cl2) mixtures. Analysis of the single-crystal X-ray diffraction data for these cocrystals revealed a gold(I)-involving two-center C-X···Au halogen bond (abbreviated as XB; X = Cl, Br) and a three-center bifurcated C-Br···(Cl-Au) XB; in the latter, the gold(I)-chloride linkage functions as an integrated XB acceptor. The noncovalent nature and energies [spanning from -1.58 to -5.52 kcal/mol for C-X···Au and -6.37 kcal/mol for C-Br···(Cl-Au) XBs] of these noncovalent interactions were studied by density functional theory calculations and topological analysis of the electron density distribution in the framework of the quantum theory of atoms-in-molecules (QTAIM) followed by noncovalent interaction (NCI) analysis at the B3LYP-D3/jorge-TZP-DKH level of theory. The nucleophilicity of the gold(I) centers toward halogens of halomethanes was verified by a set of independent methods including electrostatic potential surfaces, electron localization function projection, natural bond orbital charge transfer, electron density/electrostatic potential profile, Wiberg bond indexes, natural population analysis, and atoms-in-molecules charge analyses.

KW - NONCOVALENT INTERACTIONS

KW - ELECTRON LOCALIZATION

KW - QUANTUM-THEORY

KW - COMPLEXES

KW - MOLECULES

KW - IODINE

KW - ATOMS

KW - WEAK

KW - APPROXIMATION

KW - CHLOROFORM

UR - http://www.scopus.com/inward/record.url?scp=85124173326&partnerID=8YFLogxK

U2 - 10.1021/acs.inorgchem.1c03482

DO - 10.1021/acs.inorgchem.1c03482

M3 - Article

C2 - 35073483

AN - SCOPUS:85124173326

VL - 61

SP - 2558

EP - 2567

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 5

ER -