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

Результат исследований: Научные публикации в периодических изданияхстатьярецензирование

Аннотация

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.

Язык оригиналаанглийский
Страницы (с-по)2558-2567
Число страниц10
ЖурналInorganic Chemistry
Том61
Номер выпуска5
DOI
СостояниеОпубликовано - 7 фев 2022

Предметные области Scopus

  • Неорганическая химия
  • Физическая и теоретическая химия

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