High-Resolution Photoelectron Imaging of IrB3−: Observation of a π-Aromatic B3 + Ring Coordinated to a Transition Metal

Authors

Joseph Czekner, Brown UniversityFollow
Ling Fung Chueng, Brown UniversityFollow
G. Stephen Kocheril, Brown UniversityFollow
Maksim Kulichenko, Utah State UniversityFollow
Alexander I. Boldyrev, Utah State UniversityFollow
Lai-Sheng Wang, Brown UniversityFollow

Document Type

Article

Journal/Book Title

Angewandte Chemie international Edition

Publication Date

4-25-2019

Publisher

Wiley - V C H Verlag GmbH & Co. KGaA

Award Number

NSF, Division of Chemistry (CHE) 1664379

Funder

NSF, Division of Chemistry (CHE)

Volume

58

Issue

26

First Page

8877

Last Page

8881

Abstract

In a high‐resolution photoelectron imaging and theoretical study of the IrB₃⁻ 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 B₃ ring coordinated with the Ir atom. The isomer with the higher EA consists of a B₃ ring with a bridge‐bonded Ir atom (C_s , ²A′), and the second isomer features a tetrahedral structure (C_3v , ²A₁). The neutral tetrahedral structure was predicted to be considerably more stable than all other isomers. Chemical bonding analysis showed that the neutral C_3v isomer involves significant covalent Ir−B bonding and weak ionic bonding with charge transfer from B₃ to Ir, and can be viewed as an Ir–(η³‐B₃⁺) complex. This study provides the first example of a boron‐to‐metal charge‐transfer complex and evidence of a π‐aromatic B₃⁺ ring coordinated to a transition metal.

Recommended Citation

Czekner, J., Cheung, L. F., Kocheril, G. S., Kulichenko, M., Boldyrev, A. I., & Wang, L.-S. (2019). High-Resolution Photoelectron Imaging of IrB 3 −: Observation of a π-Aromatic B 3 + Ring Coordinated to a Transition Metal. Angewandte Chemie International Edition, 58(26), 8877–8881. https://doi.org/10.1002/anie.201902406