Precatalyst Evolution in PBiP-Pd Complexes for Electrocatalytic Proton Reduction DOI Creative Commons
Hang Cao,

Yuka Aoyama,

Kristen Mast

et al.

Published: May 8, 2024

Main-group metals as supporting ligands for transition offer potential bimetallic synergistic effects. We investigated a bismuth-palladium system utilizing PBiP pincer ligand (BiPdCl) precatalysts electrocatalytic proton reduction with thiophenol. Rinse tests revealed the formation of surface-bound active species, likely comprised Pd-based heterogenous materials. NMR and UV-visible spectroscopic studies unveiled that in diluted solutions polar coordinating solvents, chloride trans to bismuthane readily dissociates, affording solvent-coordinated species (BiPdsolvent) predominant solution species. Following thiol– solvent exchange, an equilibrium mixture solvent-bound thiolate complex (BiPdS) forms. The crystal structures BiPdS acetonitrile-coordinated model (BiPdAcN) shows thermodynamic influence ligand. Structural analysis, corroborated by computational investigations, suggests BiPdsolvent is primarily ligand-based than Pd-centered, hinting at Bi(III)–Pd(0) oxidation states rather Bi(I)–Pd(II) suggested Lewis structure BiPdsolvent. electron-rich Pd electron-poor Bi centers explain its electrochemical decomposition similar other Pd(0) Our findings shed light on electronic properties reactivities studied Bi–Pd compounds, offering example ambiguous within this system.

Language: Английский

Precatalyst Evolution in PBiP-Pd Complexes for Electrocatalytic Proton Reduction DOI Creative Commons
Hang Cao,

Yuka Aoyama,

Kristen Mast

et al.

Published: May 8, 2024

Main-group metals as supporting ligands for transition offer potential bimetallic synergistic effects. We investigated a bismuth-palladium system utilizing PBiP pincer ligand (BiPdCl) precatalysts electrocatalytic proton reduction with thiophenol. Rinse tests revealed the formation of surface-bound active species, likely comprised Pd-based heterogenous materials. NMR and UV-visible spectroscopic studies unveiled that in diluted solutions polar coordinating solvents, chloride trans to bismuthane readily dissociates, affording solvent-coordinated species (BiPdsolvent) predominant solution species. Following thiol– solvent exchange, an equilibrium mixture solvent-bound thiolate complex (BiPdS) forms. The crystal structures BiPdS acetonitrile-coordinated model (BiPdAcN) shows thermodynamic influence ligand. Structural analysis, corroborated by computational investigations, suggests BiPdsolvent is primarily ligand-based than Pd-centered, hinting at Bi(III)–Pd(0) oxidation states rather Bi(I)–Pd(II) suggested Lewis structure BiPdsolvent. electron-rich Pd electron-poor Bi centers explain its electrochemical decomposition similar other Pd(0) Our findings shed light on electronic properties reactivities studied Bi–Pd compounds, offering example ambiguous within this system.

Language: Английский

Citations

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