Ge–N Cooperativity and Catalytic Hydrodefluorination by a Pyridine Dipyrrolide Germanium Platform
Year: 2026
Type: preprint
Abstract: p-Block elements are emerging as sustainable alternatives to transition metals in catalysis, but the development of new species capable of redox cycling poses a central challenge to achieving metallomimetic reactivity. Redox-neutral processes offer a powerful strategy to circumvent challenging reductive elimination steps. Despite promising early applications of germanium(II)–ligand cooperativity for stoichiometric bond activation, the use of germylenes in redox-neutral catalysis remains largely limited to hydrofunctionalization of polar unsaturated bonds. Herein, we report the synthesis, reactivity, and catalytic application of a welldefined pyridine dipyrrolide germanium(II) complex, ( tBu PDP)Ge . Stoichiometric studies reveal that ( tBu PDP)Ge activates substrates of varying polarity, including water, N-methylaniline, ammonia-borane, and phenylsilane via a Ge–N cooperative redox-neutral mechanism that bypasses high-energy redox cycling pathways. This germylene serves as a precatalyst for the hydrodefluorination of perfluoro(hetero)arenes. Mechanistic investigations, supported by experimental and computational data, establish a redox-neutral catalytic cycle. Isolation of a well-defined germylene hydride and other key intermediates enabled development of a milder, more efficient catalytic protocol by avoiding a sluggish precatalyst activation step.
Source: ChemRxiv
Institution: Princeton University
Language: English
Subfield: Inorganic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W7211867203