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. 2022 Dec 20;52(1):11-15.
doi: 10.1039/d2dt01694j.

How reduced are nucleophilic gold complexes?

Isaac F Leach  1   2 , Diego Sorbelli  3   4 , Leonardo Belpassi  4 , Paola Belanzoni  3   4 , Remco W A Havenith  1   2   5 , Johannes E M N Klein  1
Affiliations

How reduced are nucleophilic gold complexes?

Isaac F Leach et al. Dalton Trans. .

Abstract

Nucleophilic formal gold(-I) and gold(I) complexes are investigated via Intrinsic Bond Orbital analysis and Energy Decomposition Analysis, based on density functional theory calculations. The results indicate gold(0) centres engaging in electron-sharing bonding with Al- and B- based ligands. Multiconfigurational (CASSCF) calculations corroborate the findings, highlighting the gap between the electonic structures and the oxidation state formalism.

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Conflict of interest statement

There are no conflicts to declare.

Figures

Scheme 1
Scheme 1. The nucleophilic complexes studied in this work (IPr = N,N′-bis(dipp)imidazole-2-ylidene, dipp = 2,6-iPr2C6H3), and the CO2-insertion of 1a.
Fig. 1
Fig. 1. Possible bonding scenarios, their effective gold configurations and corresponding metal oxidation states for the Au–X bond, where X is [Al(NON)] (1) or [B(o-tol)2] (2) (see Scheme 1).
Fig. 2
Fig. 2. IBOs of 1a, calculated with PBE0/def2-TZVPP//B97-3c in ORCA 5.0.2, rendered in IboView. IAO partial charge distributions indicated in parenthesis.
Fig. 3
Fig. 3. Active PM localized CASSCF(4,4) orbitals (A–D) of the Al–Au–P σ-bond in 1a, with their IAO partial charge distributions and occupation numbers shown in curved and square brackets, respectively. Calculated at the optimized B97-3c geometry in ORCA 5.0.2, rendered in IboView.
See this image and copyright information in PMC

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