Open AccessBifurcated Halogen Bonding Involving Two Rhodium(I) Centers as an Integrated σ-Hole Acceptor
Author(s) -
Anastasiya A. Eliseeva,
Daniil M. Ivanov,
Anton V. Rozhkov,
Ivan V. Ananyev,
Antonio Frontera,
Vadim Yu. Kukushkin
Publication year - 2021
Publication title -
jacs au
Language(s) - English
Resource type - Journals
ISSN - 2691-3704
DOI - 10.1021/jacsau.1c00012
Subject(s) - rhodium , halogen bond , acceptor , halogen , chemistry , nucleophile , crystallography , metal , catalysis , organic chemistry , physics , alkyl , condensed matter physics
The complexes [RhX(COD)] 2 (X = Cl, Br; COD = 1,5-cyclooctadiene) form cocrystals with σ-hole iodine donors. X-ray diffraction studies and extensive theoretical considerations indicate that the d z 2 -orbitals of two positively charged rhodium(I) centers provide sufficient nucleophilicity to form a three-center halogen bond (XB) with the σ-hole donors. The two metal centers function as an integrated XB acceptor, providing assembly via a metal-involving XB.