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High‐Resolution Photoelectron Imaging of IrB 3 − : Observation of a π‐Aromatic B 3 + Ring Coordinated to a Transition Metal
Author(s) -
Czekner Joseph,
Cheung Ling Fung,
Kocheril G. Stephen,
Kulichenko Maksim,
Boldyrev Alexander I.,
Wang LaiSheng
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201902406
Subject(s) - chemistry , crystallography , ring (chemistry) , ionic bonding , transition metal , cluster (spacecraft) , covalent bond , atom (system on chip) , metal , ion , biochemistry , organic chemistry , computer science , embedded system , programming language , catalysis
In a high‐resolution photoelectron imaging and theoretical study of the IrB 3 − cluster, two isomers were observed experimentally with electron affinities (EAs) of 1.3147(8) and 1.937(4) eV. Quantum calculations revealed two nearly degenerate isomers competing for the global minimum, both with a B 3 ring coordinated with the Ir atom. The isomer with the higher EA consists of a B 3 ring with a bridge‐bonded Ir atom ( C s , 2 A′), and the second isomer features a tetrahedral structure ( C 3 v , 2 A 1 ). The neutral tetrahedral structure was predicted to be considerably more stable than all other isomers. Chemical bonding analysis showed that the neutral C 3 v isomer involves significant covalent Ir−B bonding and weak ionic bonding with charge transfer from B 3 to Ir, and can be viewed as an Ir–(η 3 ‐B 3 + ) complex. This study provides the first example of a boron‐to‐metal charge‐transfer complex and evidence of a π‐aromatic B 3 + ring coordinated to a transition metal.