Mapping C−H×××M Interactions in Confined Spaces: (a-ICyD Me )Au, Ag, Cu Complexes Reveal 'Contra-electrostatic H-bonds' Masquerading as Anagostic Interactions
| Autor: | Guangcan Xu, Igor V. Alabugin, Sylvain Roland, Xiaolei Zhu, Olivia Bistri-Aslanoff, Matthieu Sollogoub, Gabriel dos Passos Gomes, Lise-Marie Chamoreau, Yongmin Zhang |
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| Přispěvatelé: | University of Toronto, Sorbonne Université (SU), Florida State University [Panama City], Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS) |
| Jazyk: | angličtina |
| Rok vydání: | 2021 |
| Předmět: |
C-H metal interactions
NHC Coinage metals Electron 010402 general chemistry 01 natural sciences Catalysis Metal H-bonds [CHIM]Chemical Sciences Confined space cyclodextrins 010405 organic chemistry Hydrogen bond Chemistry anagostic interactions Organic Chemistry General Chemistry Electrostatics 0104 chemical sciences coinage metals Crystallography Main group element Covalent bond visual_art visual_art.visual_art_medium Confinement |
| Zdroj: | Chemistry-A European Journal Chemistry-A European Journal, Wiley-VCH Verlag, 2021, ⟨10.1002/chem.202100263⟩ |
| ISSN: | 0947-6539 1521-3765 |
| DOI: | 10.1002/chem.202100263⟩ |
| Popis: | International audience; What happens when a C-H bond is forced to interact with unpaired pairs of electrons at a positively charged metal? Such interactions can be considered as "contra-electrostatic" H-bonds, which combine the familiar orbital interaction pattern characteristic for the covalent contribution to the conventional H-bonding with an unusual contra-electrostatic component. While electrostatics is strongly stabilizing component in the conventional C-H … X bonds where X is an electronegative main group element, it is destabilizing in the C-H … M contacts when M is Au(I), Ag(I), or Cu(I) of NHC-M-Cl systems. Such remarkable C-H … M interaction became experimentally accessible within (α-ICyD Me )MCl, NHC-Metal complexes embedded into cyclodextrins. Computational analysis of the model systems suggests that the overall interaction energies are relatively insensitive to moderate variations in the directionality of interaction between a C-H bond and the metal center, indicating stereoelectronic promiscuity of fully filled set of d -orbitals. A combination of experimental and computational data demonstrates that metal encapsulation inside the cyclodextrin cavity forces the C-H bond to point toward the metal, and reveals a still attractive "contra-electrostatic" H-bonding interaction. |
| Databáze: | OpenAIRE |
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