Molybdenum Oxo and Imido Complexes of -Diketiminate Ligands: Synthesis and Structural Aspects
详细信息 查看全文
- 作者：Ganna Lyashenko ; Regine Herbst-Irmer ; Vojtech Jancik ; Aritra Pal ; Nadia C. Mö ; sch-Zanetti
- 刊名：Inorganic Chemistry
- 出版年：2008
- 出版时间：January 7, 2008
- 年：2008
- 卷：47
- 期：1
- 页码：113 - 120
- 全文大小：157K
- 年卷期：v.47,no.1(January 7, 2008)
- ISSN：1520-510X
文摘
Treatment of [MoO2(2-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 C leads under reduction of the metal to the formation of the dimericmolybdenum(V) compound [{MoO2(NacNac)}2] (1). The compound was characterized by spectroscopic meansand by X-ray crystal structure analysis. The dimer consists of a [Mo2O4]2+ core with a short Mo-Mo bond (2.5591(5) Å) and one coordinated diketiminate ligand on each metal atom. The reaction of [MoO2(2-Pz)2] with NacNacHin benzene at room temperature leads to a mixture of 1 and the monomeric molybdenum(VI) compound [MoO2(NacNac)(2-Pz)] (2). From such solutions, yellow crystals of 2 suitable for X-ray structural analysis were obtainedrevealing the coordination of one bidentate NacNac and one 2-coordinate Pz ligand. This renders the two oxogroups inequivalent. Further high oxidation state molybdenum compounds containing the NacNac ligand wereobtained 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-coordinatecompound where the geometry is best described as trigonal-bipyramidal.