Organometallic chemistry of Pd, Ni, and Au complexes and clusters: the key to high-performance catalysis
- 1Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences
Abstract
Several liquid-phase organic reactions catalyzed by palladium, nickel, and gold precursors rarely preserve the identity, nuclearity, or electronic state of the added pre-catalyst. Molecular complexes exchange ligands and oxidation states; low-nuclearity aggregates form and fragment; nanoparticles nucleate, leach, ripen, and redeposit. The active catalyst is therefore often a reaction-dependent ensemble rather than a single structure. This Review develops a general, mechanistically explicit framework for these “cocktail” systems. It compares mononuclear complexes, metal clusters and larger nanoparticles of Pd, Ni, and Au; relates their stability to oxidative addition, reductive elimination, ligand exchange, one-electron transfer, and metal–metal bond formation; and distinguishes productive hand-offs from irreversible deactivation. Palladium most readily redistributes population across nuclearity while retaining broad access to Pd(0)/Pd(II) chemistry. Nickel encompasses a wider manifold of oxidation and spin states, but unprotected Ni(0) particles are vulnerable to oxide or hydroxide trapping. Gold is not devoid of redox catalysis: ligand-enabled Au(I)/Au(III) oxidative addition has been demonstrated, while Au(I)-Au(0) exchange can be driven by reduction, deposition, and ligand-mediated particle etching. Its cocktail behavior is therefore more narrowly defined and is largely determined by the ligand architecture and reaction class. We argue that high performance follows from population engineering: controlling the rates of release, interconversion, recapture, and loss of species. Operando population balances, rather than structural snapshots alone, are required to turn this concept into predictive catalyst design.
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BibTeX
@misc{ananikov2026organometallic,
title = {{Organometallic chemistry of Pd, Ni, and Au complexes and clusters: the key to high-performance catalysis}},
author = {Valentine P. Ananikov and Roman M. Mironenko},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15008456/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008456/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Organometallic chemistry of Pd, Ni, and Au complexes and clusters: the key to high-performance catalysis
AU - Valentine P. Ananikov
AU - Roman M. Mironenko
PY - 2026
DA - 2026/09/07
PB - ChemRxiv
DO - 10.26434/chemrxiv.15008456/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008456/v1
AB - Several liquid-phase organic reactions catalyzed by palladium, nickel, and gold precursors rarely preserve the identity, nuclearity, or electronic state of the added pre-catalyst. Molecular complexes exchange ligands and oxidation states; low-nuclearity aggregates form and fragment; nanoparticles nucleate, leach, ripen, and redeposit. The active catalyst is therefore often a reaction-dependent ensemble rather than a single structure. This Review develops a general, mechanistically explicit framework for these “cocktail” systems. It compares mononuclear complexes, metal clusters and larger nanoparticles of Pd, Ni, and Au; relates their stability to oxidative addition, reductive elimination, ligand exchange, one-electron transfer, and metal–metal bond formation; and distinguishes productive hand-offs from irreversible deactivation. Palladium most readily redistributes population across nuclearity while retaining broad access to Pd(0)/Pd(II) chemistry. Nickel encompasses a wider manifold of oxidation and spin states, but unprotected Ni(0) particles are vulnerable to oxide or hydroxide trapping. Gold is not devoid of redox catalysis: ligand-enabled Au(I)/Au(III) oxidative addition has been demonstrated, while Au(I)-Au(0) exchange can be driven by reduction, deposition, and ligand-mediated particle etching. Its cocktail behavior is therefore more narrowly defined and is largely determined by the ligand architecture and reaction class. We argue that high performance follows from population engineering: controlling the rates of release, interconversion, recapture, and loss of species. Operando population balances, rather than structural snapshots alone, are required to turn this concept into predictive catalyst design.
ER -