An Isolable One-Coordinate Lead(I) Radical with Strong g-Factor Anisotropy

Haonan Chen; Wang Chen; Dongmin Wang; Yizhen Chen; Zheng Liu; Shengfa Ye; Gengwen Tan; Song Gao

doi:10.1002/anie.202402093

An Isolable One-Coordinate Lead(I) Radical with Strong g-Factor Anisotropy

Angew Chem Int Ed Engl. 2024 Mar 4:e202402093. doi: 10.1002/anie.202402093. Online ahead of print.

Authors

Haonan Chen^{1

2}, Wang Chen^{3

4}, Dongmin Wang^{1

2}, Yizhen Chen^{1

2}, Zheng Liu¹, Shengfa Ye³, Gengwen Tan^{1

2}, Song Gao¹

Affiliations

¹ Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education, Guangdong Basic Research Center of Excellence for Functional Molecular Engineering, School of Chemistry, IGCME, Sun Yat-sen University, Guangzhou, 510275, China.
² Innovation Center for Chemical Sciences, Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, China.
³ State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian, 116023, China.
⁴ University of Chinese Academy of Sciences, Beijing, 100049, China.

PMID: 38438306
DOI: 10.1002/anie.202402093

Abstract

Lead-based radicals in the oxidation state of +1 are elusive species and are highly challenging to isolate in the condensed phase. In this study, we present the synthesis and characterization of the first isolable free plumbylyne radical 2 bearing a one-coordinate Pb(I) atom. It reacts with an N-heterocyclic carbene (NHC) to afford a two-coordinate NHC-ligated Pb(I) radical 3. 2 and 3 represent the first isolable Pb(I)-based radicals. Theoretical calculations and electron paramagnetic resonance analysis revealed that the unpaired electron mainly resides at the Pb 6p orbital in both radicals. Owing to the unique one-coordinate nature of the Pb atom in 2, it possesses two-fold orbital pseudo-degeneracy and substantial unquenched orbital angular momentum, and exhibits hitherto strongest g-factor anisotropy (g_x,y,z=1.496, 1.166, 0.683) amongst main group radicals. Preliminary investigations into the reactivity of 2 unveiled its Pb-centered radical nature, and plumbylenes were isolated as products.

Keywords: EPR; Plumbylyne; Radical; Tetrylyne; g-Factor Anisotropy.

Abstract

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