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An Isolable One‐Coordinate Lead(I) Radical with Strong g‐Factor Anisotropy
Ist Teil von
Angewandte Chemie, 2024-05, Vol.136 (20), p.n/a
Ort / Verlag
Weinheim: Wiley Subscription Services, Inc
Erscheinungsjahr
2024
Link zum Volltext
Quelle
Wiley Online Library
Beschreibungen/Notizen
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 (gx,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.
The first lead‐centered radical containing a one‐coordinate Pb atom was isolated and fully characterized. It possesses two‐fold orbital pseudo‐degeneracy and hence substantial unquenched orbital angular momentum, as manifested by hitherto strongest g‐factor anisotropy amongst main group radicals.