Lyashenko Ganna, Herbst-Irmer Regine, Jancik Vojtech, Pal Aritra, Mösch-Zanetti Nadia C
Institut für Chemie, Karl-Franzens-Universität Graz, Schubertstrasse 1, A-8010, Graz, Austria.
Inorg Chem. 2008 Jan 7;47(1):113-20. doi: 10.1021/ic701534a. Epub 2007 Dec 12.
Treatment of [MoO2(eta2-Pz)2] (Pz = 3,5-di-tert-butylpyrazolate) with the diketiminate ligand NacNacH (NacNac = CH[C(Me)NAr]2-, Ar = 2,6-Me2C6H3) at 55 degrees C leads under reduction of the metal to the formation of the dimeric molybdenum(V) compound [{MoO2(NacNac)}2] (1). The compound was characterized by spectroscopic means and by X-ray crystal structure analysis. The dimer consists of a [Mo2O4]2+ core with a short Mo-Mo bond (2.5591(5) A) and one coordinated diketiminate ligand on each metal atom. The reaction of [MoO2(eta2-Pz)2] with NacNacH in benzene at room temperature leads to a mixture of 1 and the monomeric molybdenum(VI) compound [MoO2(NacNac)(eta2-Pz)] (2). From such solutions, yellow crystals of 2 suitable for X-ray structural analysis were obtained revealing the coordination of one bidentate NacNac and one eta2-coordinate Pz ligand. This renders the two oxo groups inequivalent. Further high oxidation state molybdenum compounds containing the NacNac ligand were obtained by the reaction of [Mo(NAr)2Cl2(dme)] (Ar = 2,6-Me2C6H3) and [Mo(N-t-Bu)2Cl2(dme)] (dme = dimethoxyethane) with 1 equiv of the potassium salt NacNacK forming [Mo(NAr)2Cl(NacNac)] (3) and [Mo(N-t-Bu)2Cl(NacNac)] (4), respectively, in good yields. The X-ray structure analysis of 3 revealed a penta-coordinate compound where the geometry is best described as trigonal-bipyramidal.
在55摄氏度下，用二酮亚胺配体NacNacH（NacNac = CH[C(Me)NAr]2-，Ar = 2,6-Me2C6H3）处理[MoO2(η2-Pz)2]（Pz = 3,5-二叔丁基吡唑酸酯），在金属还原的情况下会生成二聚钼(V)化合物[{MoO2(NacNac)}2]（1）。该化合物通过光谱手段和X射线晶体结构分析进行了表征。二聚体由一个[Mo2O4]2+核心组成，Mo-Mo键较短（2.5591(5) Å），每个金属原子上有一个配位的二酮亚胺配体。[MoO2(η2-Pz)2]与NacNacH在室温下于苯中反应，会生成1和单体钼(VI)化合物[MoO2(NacNac)(η2-Pz)]（2）的混合物。从这些溶液中获得了适合进行X射线结构分析的2的黄色晶体，揭示了一个双齿NacNac和一个η2配位的Pz配体的配位情况。这使得两个氧代基团不等价。通过[Mo(NAr)2Cl2(dme)]（Ar = 2,6-Me2C6H3）和[Mo(N-t-Bu)2Cl2(dme)]（dme = 二甲氧基乙烷）与1当量的钾盐NacNacK反应，分别以良好的产率得到了含有NacNac配体的进一步的高氧化态钼化合物[Mo(NAr)2Cl(NacNac)]（3）和[Mo(N-t-Bu)2Cl(NacNac)]（4）。3的X射线结构分析表明这是一个五配位化合物，其几何形状最好描述为三角双锥。
