An Isolable One-Coordinate Lead(I) Radical with Strong g-Factor Anisotropy.
Angew Chem Int Ed Engl
; 63(20): e202402093, 2024 May 13.
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| ID: mdl-38438306
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 (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.
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