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<p>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, [Ni<sub>4</sub>H<sub>4</sub>(P<sup><i>t</i></sup>Bu<sub>3</sub>)<sub>4</sub>] (<b>1</b>), which we synthesize by reacting [Li(THF)<sub><i>x</i></sub>][Ni{N(SiMe<sub>3</sub>)<sub>2</sub>}<sub>3</sub>] (<i>x</i> ≈ 4.5 − 5) with pinacolborane (HBpin) in the presence of tri-<i>tert</i>-butylphosphine (P<sup><i>t</i></sup>Bu<sub>3</sub>). Its molecular structure features a tetrahedral Ni<sub>4</sub> core, with four face-capping <i>μ</i><sub>3</sub>-hydrides and four terminally bound P<sup><i>t</i></sup>Bu<sub>3</sub> ligands. Cluster <b>1</b> is capable of reversible C–H and C–D bond cleavage of benzene-<i>d</i><sub>6</sub>, toluene-<i>d</i><sub>8</sub>, <i>n</i>-octane-<i>d</i><sub>18</sub>, and its own P<sup><i>t</i></sup>Bu<sub>3</sub> ligands at 50 °C, leading to H/D exchange between the deuterated solvents and the ligands in <b>1</b>. This reactivity is further utilized in the catalytic hydrogen isotope exchange reaction between benzene-<i>d</i><sub>6</sub> and toluene. The reversible dissociation of one P<sup><i>t</i></sup>Bu<sub>3</sub> ligand in <b>1</b> 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 P<sup><i>t</i></sup>Bu<sub>3</sub> ligands in <b>1</b> as the key step in triggering C–H and C–D bond activation.</p>

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A tetranuclear nickel hydride cluster capable of reversible activation of aromatic and aliphatic C–H bonds

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  • 发表日期：

    2026年7月29日

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  • Kohei Sunami,
  • Tatsuya Higaki,
  • Kanata Tanaka,
  • Ryotaro Yamanashi,
  • W. M. C. Sameera,
  • Ryo Takahata,
  • Toshiharu Teranishi,
  • Soichi Kikkawa,
  • Seiji Yamazoe,
  • Takuya Shiga,
  • Masayuki Nihei,
  • Tatsuhisa Kato,
  • Hitoshi Izu,
  • Yasuhiro Ohki

摘要

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.