A Nickel–Capped Calcium Hydride: Implications for Diene Hydrometallation
- 1Department of Chemistry, Western University, 1151 Richmond Street, London, Canada, N8K 3G6
- 2Department of Chemistry and Biochemistry, Wilfrid Laurier University, 75 University Ave. W., Waterloo, Canada, N2L 3C5
- 3Department of Chemistry, Imperial College London, Molecular Sciences Research Hub, 82 Wood Lane, London, United Kingdom, W12 0BZ
Abstract
We report here the synthesis and comprehensive characterization of a molecular nickel complex featuring a σ–[Ca–H–Ni] interaction. Although numerous σ–[E–H–M] species have been characterized, analogous complexes featuring heavier alkaline–earth hydrides remain exceptionally rare owing to their highly ionic and reactive nature. Reaction of [Ni(t,t,t–cdt)] (t,t,t–cdt = t,t,t–cyclododeca–1,5,9–triene) with the calcium hydride, [{(DippBDI)Ca(THF)}(μ–H)]2 affords [{(DippBDI)Ca(THF)(μ–H){Ni(t,t,t–cdt)}], representing the first well–defined Ca–H–M complex (where M = transition metal) characterized in both the solution– and solid–state. Multinuclear NMR spectroscopy, single–crystal X–ray diffraction, and computational studies collectively establish the presence and electronic structure of a σ–[Ca–H–Ni] unit, revealing a polarized interaction in which the hydride is primarily associated with nickel, while retaining a significant interaction with calcium. The isolation of this σ–[Ca–H–Ni] adduct provides a molecular framework for understanding cooperative reactivity between calcium hydrides and nickel. We show that this and related σ–[Ca–H–Ni] species are likely intermediates in the nickel–promoted hydrometallation of non–activated dienes.
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BibTeX
@misc{salic2026nickelcapped,
title = {{A Nickel–Capped Calcium Hydride: Implications for Diene Hydrometallation}},
author = {Sandra Salic and A. Dina Dilinaer and Gabriel J. Jobin and Louise N. Dawe and Mark R. Crimmin and Marcus W. Drover},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15010815/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010815/v1},
note = {CC BY-NC-ND},
}
RIS
TY - UNPB
TI - A Nickel–Capped Calcium Hydride: Implications for Diene Hydrometallation
AU - Sandra Salic
AU - A. Dina Dilinaer
AU - Gabriel J. Jobin
AU - Louise N. Dawe
AU - Mark R. Crimmin
AU - Marcus W. Drover
PY - 2026
DA - 2026/10/21
PB - ChemRxiv
DO - 10.26434/chemrxiv.15010815/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010815/v1
AB - We report here the synthesis and comprehensive characterization of a molecular nickel complex featuring a σ–[Ca–H–Ni] interaction. Although numerous σ–[E–H–M] species have been characterized, analogous complexes featuring heavier alkaline–earth hydrides remain exceptionally rare owing to their highly ionic and reactive nature. Reaction of [Ni(t,t,t–cdt)] (t,t,t–cdt = t,t,t–cyclododeca–1,5,9–triene) with the calcium hydride, [{(DippBDI)Ca(THF)}(μ–H)]2 affords [{(DippBDI)Ca(THF)(μ–H){Ni(t,t,t–cdt)}], representing the first well–defined Ca–H–M complex (where M = transition metal) characterized in both the solution– and solid–state. Multinuclear NMR spectroscopy, single–crystal X–ray diffraction, and computational studies collectively establish the presence and electronic structure of a σ–[Ca–H–Ni] unit, revealing a polarized interaction in which the hydride is primarily associated with nickel, while retaining a significant interaction with calcium. The isolation of this σ–[Ca–H–Ni] adduct provides a molecular framework for understanding cooperative reactivity between calcium hydrides and nickel. We show that this and related σ–[Ca–H–Ni] species are likely intermediates in the nickel–promoted hydrometallation of non–activated dienes.
ER -