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. 2023 Jun 28;145(25):13758-13767.
doi: 10.1021/jacs.3c02223. Epub 2023 Jun 12.

Four-Electron Reduction of O2 Using Distibines in the Presence of ortho-Quinones

Benyu Zhou  1 , François P Gabbaï  1
Affiliations

Four-Electron Reduction of O2 Using Distibines in the Presence of ortho-Quinones

Benyu Zhou et al. J Am Chem Soc. .

Abstract

This study, which aims to identify atypical platforms for the reduction of dioxygen, describes the reaction of O2 with two distibines, namely, 4,5-bis(diphenylstibino)-2,7-di-tert-butyl-9,9-dimethylxanthene and 4,5-bis(diphenylstibino)-2,7-di-tert-butyl-9,9-dimethyldihydroacridine, in the presence of an ortho-quinone such as phenanthraquinone. The reaction proceeds by oxidation of the two antimony atoms to the + V state in concert with reductive cleavage of the O2 molecule. As confirmed by 18O labeling experiments, the two resulting oxo units combine with the ortho-quinone to form an α,α,β,β-tetraolate ligand that bridges the two antimony(V) centers. This process, which has been studied both experimentally and computationally, involves the formation of asymmetric, mixed-valent derivatives featuring a stibine as well as a catecholatostiborane formed by oxidative addition of the quinone to only one of the antimony centers. Under aerobic conditions, the catecholatostiborane moiety reacts with O2 to form a semiquinone/peroxoantimony intermediate, as supported by NMR spectroscopy in the case of the dimethyldihydroacridine derivative. These intermediates swiftly evolve into the symmetrical bis(antimony(V)) α,α,β,β-tetraolate complexes via low barrier processes. Finally, the controlled protonolysis and reduction of the bis(antimony(V)) α,α,β,β-tetraolate complex based on the 9,9-dimethylxanthene platform have been investigated and shown to regenerate the starting distibine and the ortho-quinone. More importantly, these last reactions also produce two equivalents of water as the product of O2 reduction.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Selected Reactions of Group 15 Compounds with O2
Figure 1
Figure 1
Synthesis and solid-state structures of 1O or 1NH.
Figure 2
Figure 2
Top: reactions of distibines 1O and 1NH with phenQ. Bottom: portions of the 1H NMR spectra (red trace: 1O or 1NH; orange trace: phenQ; and green trace: 2O or 2NH) of 1:5 mixtures of 1O (left) or 1NH (right) and phenQ in CDCl3 under N2.
Figure 3
Figure 3
Reaction of 1O and 1NH with phenQ in air, leading to the formation of 3O and 3NH. The crystal structure of 3O is also displayed along with the ESI mass spectrum of unlabeled and 18O-labeled 3NH.
Figure 4
Figure 4
Top: synthesis of 4O and 4NH by the reaction of 1O and 1NH, respectively, with pyrene-4,5-dione in air. One of the independent molecules in the crystal structure of 4NH is also shown. Middle: reactions of 1O and 1NH with phenQ under O2 monitored by 1H NMR. Bottom: portions of the 1H NMR spectra (red trace: 1O or 1NH; orange trace: phenQ; green trace: 2O or 2NH; blue trace: 3O or 3NH; magenta trace: IntNH) of 1:1 mixtures of phenQ and 1O (left) or 1NH (right) in CDCl3 under a N2 atmosphere, 5 min and 2 h after exposure to O2. The spectra of pure 3O and 3NH in CDCl3 are also included for reference.
Figure 5
Figure 5
Computed pathway for the isomerization of the putative phenSQ peroxide intermediate into the corresponding phenanthrene-9,9,10,10-tetraolate. Gas-phase optimization and frequency computations of all structures were performed with M06-2X functional and mixed basis sets: def2-svp for C, H, N, O, and aug-cc-pVTZ-PP for Sb. Single-point energy calculations were carried out on the gas-phase-optimized structures using the RI-PWPB95-D3(BJ)/def2-tzvpp method with the SMD solvation model using CH2Cl2 as the solvent.
Chart 1
Chart 1. Structure of Complex H
Figure 6
Figure 6
Acidolysis and reduction of 3O. The structure of the oxo-bridged species 5O, formed in the reaction, is also shown.
See this image and copyright information in PMC

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