A Lead(II) Substituted Triplet Carbene

Fabian Dankert; Julian Messelberger; Ugo Authesserre; Abinash Swain; David Scheschkewitz; Bernd Morgenstern; Dominik Munz

doi:10.1021/jacs.4c10205

A Lead(II) Substituted Triplet Carbene

J Am Chem Soc. 2024 Oct 30;146(43):29630-29636. doi: 10.1021/jacs.4c10205. Epub 2024 Oct 18.

Authors

Fabian Dankert¹, Julian Messelberger¹, Ugo Authesserre¹, Abinash Swain¹, David Scheschkewitz², Bernd Morgenstern³, Dominik Munz¹

Affiliations

¹ Saarland University, Coordination Chemistry, Campus C4.1, D-66123 Saarbrücken, Germany.
² Saarland University, Inorganic and General Chemistry, Campus C4.1, D-66123 Saarbrücken, Germany.
³ Saarland University, Inorganic Solid-State Chemistry, Campus C4.1, D-66123 Saarbrücken, Germany.

Abstract

Reaction of the pincer-type ligand L₃ supported complex [L₃PbBr][BArF₂₄] (1) with Li[(C(═N₂)TMS)] furnishes [L₃Pb(C(═N₂)TMS)][BArF₂₄] (2). Diazo-compound 2 eliminates dinitrogen upon irradiation affording formal plumba-alkyne 3, which persists in cold fluoroarene solutions. Variable temperature UV/Vis and NMR spectroscopies in combination with quantum-chemical calculations identify 3 as a metal-substituted triplet carbene. In-crystallo irradiation of [L₃Pb(C(═N₂)TMS)(tol)][BArF₂₄] (2·tol) provides a snapshot of intermolecular C-H bond insertion with toluene (4).