A tetranuclear nickel hydride cluster capable of reversible activation of aromatic and aliphatic C–H bonds
Journal article, 2026
Metal cluster complexes supported by multiple hydrides are useful for activating inert bonds and molecules, while nickel-based variants capable of activating external substrates remain scarce. Here, we report a tetranuclear Ni-hydride-phosphine cluster, [Ni4H4(PtBu3)4] (1), which we synthesize by reacting [Li(THF)x][Ni{N(SiMe3)2}3] (x ≈ 4.5 − 5) with pinacolborane (HBpin) in the presence of tri-tert-butylphosphine (PtBu3). Its molecular structure features a tetrahedral Ni4 core, with four face-capping μ3-hydrides and four terminally bound PtBu3 ligands. Cluster 1 is capable of reversible C–H and C–D bond cleavage of benzene-d6, toluene-d8, n-octane-d18, and its own PtBu3 ligands at 50 °C, leading to H/D exchange between the deuterated solvents and the ligands in 1. This reactivity is further utilized in the catalytic hydrogen isotope exchange reaction between benzene-d6 and toluene. The reversible dissociation of one PtBu3 ligand in 1 is proposed as the key step to trigger the C–H and C–D bond activation. Quantum chemical computations propose the reversible displacement of one of the PtBu3 ligands in 1 as the key step in triggering C–H and C–D bond activation.
Author
Kohei Sunami
Kyoto University
Tatsuya Higaki
Kyoto University
Tokyo Metropolitan University
Kanata Tanaka
Kyoto University
Ryotaro Yamanashi
Kyoto University
Chamil Sameera Wickramarachchi Millawalage
Chalmers, Space, Earth and Environment, Astronomy and Plasmaphysics
Ryo Takahata
Kyoto University
Toshiharu Teranishi
Kyoto University
Soichi Kikkawa
Tokyo Metropolitan University
Seiji Yamazoe
Tokyo Metropolitan University
Takuya Shiga
University of Tsukuba
Masayuki Nihei
University of Tsukuba
Tatsuhisa Kato
Kyoto University
Hitoshi Izu
Kyoto University
Yasuhiro Ohki
Kyoto University
Nature Communications
2041-1723 (ISSN) 20411723 (eISSN)
Vol. 17 1 7259Subject Categories (SSIF 2025)
Theoretical Chemistry
DOI
10.1038/s41467-026-76006-4