Work

Two-fold proton coupled electron transfer of a Ta( v ) aniline complex mediated by a redox active NNN pincer ligand

Year: 2024

Type: article

Abstract: We report the proton-coupled electron transfer (PCET) reactivity of an octahedral Ta(V) aniline complex supported by an acridane-derived redox active NNN pincer ligand. The reversible binding of aniline to a Ta(V) dichloride induces significant coordination-induced bond weakening (CIBW) of the aniline N-H bonds. This enables a rare two-fold hydrogen atom abstraction, resulting in a terminal imido complex and a two-electron oxidation of the NNN pincer ligand, all while maintaining the metal's oxidation state. The bond dissociation free energies (BDFEs) of the aniline and a transient radical amido complex are estimated through stoichiometric reactions with different hydrogen atom abstractors and donors, further supported by density functional theory calculations.

Source: Dalton Transactions

DOI: 10.1039/d4dt03281k

Authors: Sotirios Pavlidis, Jasmin Alasadi, Amanda Opis-Basilio, Josh Abbenseth

Institution: Humboldt-Universität zu Berlin

Language: English

Topic: Organometallic Complex Synthesis and Catalysis

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Funders: Fonds der Chemischen Industrie, Deutsche Forschungsgemeinschaft, Einstein Stiftung Berlin, Humboldt-Universität zu Berlin

Awards: G1117759237, EXC 2008: Unifying Systems in Catalysis "UniSysCat", G6637249919, G8136362559