Understanding the steric demand of the reactions of nickel(0) complexes with aryl halide substrates
Abstract
Nickel complexes are able to undergo reactions with organohalides by a variety of fundamental steps, which can be either one-electron or two-electron in nature. Two electron processes are typically some flavour of oxidative addition (OA), but various mechanisms have been proposed for the one-electron reactions, including inner-sphere halogen atom abstraction (HAA) and outer-sphere single electron transfer (SET). It was recently proposed that the steric bulk of a substrate can be used as an indicator of whether HAA is feasible, and therefore that SET was in operation for a specific and bulky substrate. However, the steric requirements for HAA by nickel have not yet been systematically assessed. Here we report a structured assessment of how HAA feasibility might vary with ligand and substrate steric impact. We find that HAA by [Ni(PMe 3 ) 3 ] is feasible even for sterically very hindered substrates. Systems with ferrocene-derived bisphosphine ligands tend to prefer HAA when the ligand and/or the substrate are very sterically bulky.
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BibTeX
@misc{listyarini2026understanding,
title = {{Understanding the steric demand of the reactions of nickel(0) complexes with aryl halide substrates}},
author = {Risnita Vicky Listyarini and Ryan Oliver and Hio U. Lao and David J. Nelson},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15009547/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009547/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Understanding the steric demand of the reactions of nickel(0) complexes with aryl halide substrates
AU - Risnita Vicky Listyarini
AU - Ryan Oliver
AU - Hio U. Lao
AU - David J. Nelson
PY - 2026
DA - 2026/09/28
PB - ChemRxiv
DO - 10.26434/chemrxiv.15009547/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009547/v1
AB - Nickel complexes are able to undergo reactions with organohalides by a variety of fundamental steps, which can be either one-electron or two-electron in nature. Two electron processes are typically some flavour of oxidative addition (OA), but various mechanisms have been proposed for the one-electron reactions, including inner-sphere halogen atom abstraction (HAA) and outer-sphere single electron transfer (SET). It was recently proposed that the steric bulk of a substrate can be used as an indicator of whether HAA is feasible, and therefore that SET was in operation for a specific and bulky substrate. However, the steric requirements for HAA by nickel have not yet been systematically assessed. Here we report a structured assessment of how HAA feasibility might vary with ligand and substrate steric impact. We find that HAA by [Ni(PMe 3 ) 3 ] is feasible even for sterically very hindered substrates. Systems with ferrocene-derived bisphosphine ligands tend to prefer HAA when the ligand and/or the substrate are very sterically bulky.
ER -