Bis(tert-butoxi)alan (tBu-O)₂AlH reagiert mit Nickeldiacetylacetonat bei höheren Temperaturen zum neuartigen Nickel-Aluminium-Sauerstoff-Cluster [Ni(acac)OAl(OtBu)₂]₄; neben anderen Produkten wird auch Aluminiumtriacetylacetonat Al(acac)₃ gebildet. Der Metall-Sauerstoff-Cluster lässt sich durch Kristallisation isolieren und kann über Röntgenstrukturanalyse charakterisiert werden. Das Molekül [Ni(acac)OAl(OtBu)₂]₄ enthält im Zentrum einen achtgliedrigen Al₄O₄-Ring, an den acht kantenverknüpfte NiO₂Al-Ringe über gemeinsame O-Al-O-Einheiten gebunden sind. Die Punktsymmetrie des Metall-Sauerstoff-Clusters beträgt nahezu S₄. Während die Aluminiumatome verzerrt tetraedrisch von Sauerstoffatomen umgeben sind (mittlerer Abstände Al-O zwischen 1, 730(6) und 1, 789(6) Å)), befinden sich die Nickelatome in verzerrt quadratisch pyramidalen Sauerstoff-Koordinationssphären (Ni-O_axial = 1, 938(6) Å, Ni-O_basal = 2, 056(9)Å). Die Nickelatome sind in einem Highspin-d⁸-Zustand (μ_eff = 3, 32 B.M.).

Abstract

A New Aluminum/Nickel/Oxo-Cluster: [Ni(acac)OAl(OtBu)₂]₄

When bis(tert-butoxy)alane (tBu-O)₂AlH is allowed to react with nickeldiacetylacetonate at elevated temperature a new nickel/aluminum/oxo cluster [Ni(acac)OAl(OtBu)₂]₄ is formed together with aluminum acetylacetonate Al(acac)₃ and some other products. The metal/oxo cluster is isolated by crystallization and structurally fully characterized by X-ray diffraction analysis. The molecule [Ni(acac)OAl(OtBu)₂]₄ contains an eight membered Al₄O₄ cycle, to which eight mutually edge sharing NiO₂Al cycles are fused. The overall point symmetry of the metal/oxo cluster is almost S₄. While the aluminum atoms are tetrahedrally surrounded by oxygen ligands (mean distances Al-O in-between 1, 730(6) and 1, 789(6) Å)), the nickel atoms are in a square pyramidal coordination sphere of oxygen atoms (Ni-O_axial = 1.938(6) Å, Ni-O_basal = 2.056(9) Å; all polyhedra are distorted). The nickel atoms have a d⁸ high spin electron configuration (μ_eff = 3.32 B.M.).

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Volume629, Issue3

March 2003

Pages 569-574

Ein neuer Aluminium/Nickel/Oxo-Cluster: [Ni(acac)OAl(OtBu)₂]₄^†

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Ein neuer Aluminium/Nickel/Oxo-Cluster: [Ni(acac)OAl(OtBu)₂]₄^†