title: A reduced β-diketiminato-ligated Ni3H4 unit catalyzing H/D exchange.
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.
authors.affiliation: Humboldt-Universität zu Berlin, Institut für Chemie, Brook-Taylor-Strasse 2, 12489 Berlin, Germany.
authors.forename: Stefan
authors.initials: S
authors.lastname: Pfirrmann
authors.forename: Christian
authors.initials: C
authors.lastname: Limberg
authors.forename: Christian
authors.initials: C
authors.lastname: Herwig
authors.forename: Christina
authors.initials: C
authors.lastname: Knispel
authors.forename: Beatrice
authors.initials: B
authors.lastname: Braun
authors.forename: Eckhard
authors.initials: E
authors.lastname: Bill
authors.forename: Reinhard
authors.initials: R
authors.lastname: Stösser
mesh_terms: D002384:Catalysis; D018360:Crystallography, X-Ray; D003903:Deuterium / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D008280:Magnetics; D008958:Models, Molecular; D056004:Molecular Dynamics Simulation; D009532:Nickel / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010084:Oxidation-Reduction
chemical_list: D009942:Organometallic Compounds; D009532:Nickel; D006859:Hydrogen; D003903:Deuterium