Visible light-induced palladium-carbon bond weakening in catalytically relevant T-shaped complexes

Peter M. Waddell, Lei Tian, Anthony R. Scavuzzo, Lalu Venigalla, Gregory D. Scholes, Brad P. Carrow

Research output: Contribution to journalArticlepeer-review

1 Scopus citations

Abstract

Triggering one-electron redox processes during palladium catalysis holds the potential to unlock new reaction mechanisms and synthetic methods not previously accessible in the typical two-electron reaction manifolds that dominate palladium catalysis. We report that T-shaped organopalladium(ii) complexes coordinated by a bulky monophosphine, a class of organometallic intermediate featured in a range of contemporary catalytic reactions, undergo blue light-promoted bond weakening leading to mild and efficient homolytic cleavage of strong Pd(ii)-C(sp3) bonds under ambient conditions. The origin of light-triggered radical formation in these systems, which lack an obvious ligand-based chromophore (i.e., π-systems), was investigated using a combination of DFT calculations, photoactinometry, and transient absorption spectroscopy. The available data suggest T-shaped organopalladium(ii) complexes manifest unusual blue light-accessible Pd-to-C(sp3) transition. The quantum efficiency and excited state lifetime of this process were unexpectedly superior compared to a prototypical (α-diimine)Pd(ii) complex featuring a low-lying, ligand-centered LUMO (π*). These results suggest coordinatively-unsaturated organopalladium(ii) compounds, catalysts in myriad catalytic processes, have untapped potential for one-electron reactivity under visible light excitation.

Original languageEnglish (US)
Pages (from-to)14217-14228
Number of pages12
JournalChemical Science
Volume14
Issue number48
DOIs
StatePublished - Nov 28 2023

All Science Journal Classification (ASJC) codes

  • General Chemistry

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