Article

A reduced β-diketiminato-ligated Ni3H4 unit catalyzing H/D exchange.

Humboldt-Universität zu Berlin, Institut für Chemie, Brook-Taylor-Strasse 2, 12489 Berlin, Germany.
Journal of the American Chemical Society (Impact Factor: 10.68). 10/2010; 132(39):13684-91. DOI: 10.1021/ja106266v
Source: PubMed

ABSTRACT An investigation concerning the stepwise reduction of the β-diketiminato nickel(II) hydride dimer [LNi(μ-H)(2)NiL], 1 (L = [HC(CMeNC(6)H(3)(iPr)(2))(2)](-)), has been carried out. While the reaction with one equivalent of potassium graphite, KC(8), led to the mixed valent Ni(I)/Ni(II) complex K[LNi(μ-H)(2)NiL], 3, treatment of 1 with two equivalents of KC(8) surprisingly yielded in the trinuclear complex K(2)[LNi(μ-H)(2)Ni(μ-H)(2)NiL], 4, in good yields. The Ni(3)H(4) core contains one Ni(II) and two Ni(I) centers, which are antiferromagnetically coupled so that a singlet ground state results. 4 represents the first structurally characterized molecular compound with three nickel atoms bridged by hydride ligands, and it shows a very interesting chemical behavior: Single-electron oxidation yields in the Ni(II)(2)Ni(I) compound K[LNi(μ-H)(2)Ni(μ-H)(2)NiL], 5, and treatment with CO leads to the elimination of H(2) with formation of the carbonyl complex K(2)[LNi(CO)](2), 6. Beyond that, it could be shown that 4 undergoes H/D exchange with deuterated solvents and the deuteride-compound 4-D(4) reacts with H(2) to give back 4. The crystal structures of the novel compounds 3-6 have been determined, and their electronic structures have been investigated by EPR and NMR spectroscopy, magnetic measurements, and DFT calculations.

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