Pairwise H₂/D₂ Exchange and H₂ Substitution at a Bimetallic Dinickel(II) Complex Featuring Two Terminal Hydrides

A compartmental ligand scaffold HL with two β-diketiminato binding sites spanned by a pyrazolate bridge gave a series of dinuclear nickel(II) dihydride complexes M[LNi₂(H)₂], M = Na (Na·2) and K (K·2), which were isolated after reacting the precursor complex [LNi₂(μ-Br)] (1) with MHBEt₃ (M = Na and K). Crystallographic characterization showed the two hydride ligands to be directed into the bimetallic pocket, closely interacting with the alkali metal cation. Treatment of K·2 with dibenzo(18-crown-6) led to the separated ion pair [LNi₂(H)₂][K(DB18C6)] (2[K(DB18C6)]). Reaction of Na·2 or K·2 with D₂ was investigated by a suite of ¹H and ²H NMR experiments, revealing an unusual pairwise H₂/D₂ exchange process that synchronously involves both Ni-H moieties without H/D scrambling. A mechanistic picture was provided by DFT calculations which suggested facile recombination of the two terminal hydrides within the bimetallic cleft, with a moderate enthalpic barrier of ∼62 kJ/mol, to give H₂ and an antiferromagnetically coupled [LNi^I₂]^- species. This was confirmed by SQUID monitoring during H₂ release from solid 2[K(DB18C6)]. Interaction with the Lewis acid cation (Na⁺ or K⁺) significantly stabilizes the dihydride core. Kinetic data for the M[L(Ni-H)₂] → H₂ transition derived from 2D ¹H EXSY spectra confirmed first-order dependence of H₂ release on M·2 concentration and a strong effect of the alkali metal cation M⁺. Treating [LNi₂(D)₂]^- with phenylacetylene led to D₂ and dinickel(II) complex 3^- with a twice reduced styrene-1,2-diyl bridging unit in the bimetallic pocket. Complexes [LNi^II₂(H)₂]^- having two adjacent terminal hydrides thus represent a masked version of a highly reactive dinickel(I) core. Storing two reducing equivalents in adjacent metal hydrides that evolve H₂ upon substrate binding is reminiscent of the proposed N₂ binding step at the FeMo cofactor of nitrogenase, suggesting the use of the present bimetallic scaffold for reductive bioinspired activation of a range of inert small molecules.