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A Lead(II) Substituted Triplet Carbene

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

2024Journal of the American Chemical Society20 citationsDOIOpen Access PDF

Abstract

High Resolution Image Download MS PowerPoint Slide Reaction of the pincer-type ligand L 3 supported complex [L 3 PbBr][BArF 24 ] ( 1 ) with Li[(C(═N 2 )TMS)] furnishes [L 3 Pb(C(═N 2 )TMS)][BArF 24 ] ( 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 [L 3 Pb(C(═N 2 )TMS)(tol)][BArF 24 ] ( 2 ·tol) provides a snapshot of intermolecular C–H bond insertion with toluene ( 4 ).

Topics & Concepts

ChemistryCarbeneLead (geology)StereochemistryComputational chemistryPhotochemistryOrganic chemistryCatalysisGeologyGeomorphologyN-Heterocyclic Carbenes in Organic and Inorganic ChemistryCatalytic Cross-Coupling ReactionsOrganometallic Complex Synthesis and Catalysis
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