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PreprintCC BYChemRxiv

Ge–N Cooperativity and Catalytic Hydrodefluorination by a Pyridine Dipyrrolide Germanium Platform

  • Isabelle Fejes1,2
  • Alessio Regni1,2
  • Yumeng Liao1,2
  • Charles J. Ambach1,2
  • Javier M. Hurst1,2
  • Aleksandr Knyazev1,2
  • Jose B. Roque1,2
  1. 1Department of Chemistry
  2. 2Princeton University
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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.

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Cite

BibTeXRIS
BibTeX
@misc{fejes2026cooperativity,
  title = {{Ge–N Cooperativity and Catalytic Hydrodefluorination by a Pyridine Dipyrrolide Germanium Platform}},
  author = {Isabelle Fejes and Alessio Regni and Yumeng Liao and Charles J. Ambach and Javier M. Hurst and Aleksandr Knyazev and Jose B. Roque},
  howpublished = {ChemRxiv},
  year = {2026},
  month = sep,
  doi = {10.26434/chemrxiv.15008387/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008387/v1},
  note = {CC BY},
}
RIS
TY  - UNPB
TI  - Ge–N Cooperativity and Catalytic Hydrodefluorination by a Pyridine Dipyrrolide Germanium Platform
AU  - Isabelle Fejes
AU  - Alessio Regni
AU  - Yumeng Liao
AU  - Charles J. Ambach
AU  - Javier M. Hurst
AU  - Aleksandr Knyazev
AU  - Jose B. Roque
PY  - 2026
DA  - 2026/09/07
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15008387/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008387/v1
AB  - 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.
ER  -