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. 2023 Mar 3;1(3):175-182.
doi: 10.1021/prechem.3c00003. eCollection 2023 May 22.

Atomically Precise Metal Nanoclusters as Single Electron Transferers for Hydroborylation

Wanli Zhu  1   2 , Sheng Zhang  1   2 , Weigang Fan  1   2 , Ying Yang  3 , Hongliang Zhao  1   2 , Wenwen Fei  1   2 , Hong Bi  4 , Jian He  5   6 , Man-Bo Li  1   2 , Zhikun Wu  1   2
Affiliations

Atomically Precise Metal Nanoclusters as Single Electron Transferers for Hydroborylation

Wanli Zhu et al. Precis Chem. .

Abstract

The emergence of metal nanoclusters with atomically precise compositions and structures provides an opportunity for in-depth investigation of catalysis mechanisms and structure-property correlations at the nanoscale. However, a serious problem for metal nanocluster catalysts is that the ligands inhibit the catalytic activity through deactivating the surface of the nanoclusters. Here, we introduce a novel catalytic mode for metal nanoclusters, in which the nanoclusters initiate the catalysis via single electron transfer (SET) without destroying the integrity of nanoclusters, providing a solution for the contradiction between activity and stability of metal nanoclusters. We illustrated that the novel activation mode featured low catalyst loading (0.01 mol %), high TOF, mild reaction conditions, and easy recycling of catalyst in alkyne hydroborylation, which often suffered from poor selectivity, low functional group tolerance, etc. Furthermore, the catalyst [Au1Cu14(TBBT)12(PPh3)6]+ (TBBTH: p-tert-butylthiophenol) can be applied in highly efficient tandem processes such as hydroborylation-deuteration and hydroborylation-isomerization, demonstrating the utility of the introduced activation mode for metal nanoclusters.

Keywords: atomically precise metal nanocluster; boryl radical; hydroborylation; single electron transfer; tandem catalysis.

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Figures

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1. Previous Works on Metal-Catalyzed Hydroborylations (a) and This Work on Nanocluster-Catalyzed Hydroborylation (b)
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(a) Model hydroborylation reaction. (b) Structure of Au1Cu14; carbon and hydrogen atoms are all omitted for clarity. (c) UV–vis spectra of Au1Cu14 before and after catalytic reaction.
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Mechanism studies. (a) DPV spectra of B2pin2, [B2pin2 + K2CO3], and 4d. (b) Radical trapping experiments. (c) EPR spectra of [DMPO + 4d + B2pin2] and [DMPO + B2pin2]. (d) 11B NMR spectra of [4d + B2pin2] and B2pin2. (e) 19F NMR spectra of [4d + 4-FPhCCH] and 4-FPhCCH. (f) Proposed mechanism.
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2. Substrate Scope and Catalyst Recovery
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3. Applications of Au1Cu14SPh t Bu-Catalyzed Alkyne Hydroborylation: (a) Gram-Scale Synthesis, (b) One-Pot Late-Stage Functionalizations, (c) Deuterated Products, and (d) Configuration Inversion under Irradiation with Blue LED
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