Tetranuclear Zirconium and Hafnium Polyhydride Complexes Composed of the 鈥淐pMH2鈥?Units

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• 作者：Shaowei Hu ; Takanori Shima ; Yi Luo ; Zhaomin Hou
• 刊名：Organometallics
• 出版年：2013
• 出版时间：April 8, 2013
• 年：2013
• 卷：32
• 期：7
• 页码：2145-2151
• 全文大小：373K
• 年卷期：v.32,no.7(April 8, 2013)
• ISSN：1520-6041

文摘

A series of tetranuclear group 4 transition metal octahydride complexes [(C₅Me₄R)₄M₄(渭-H)₈] (2-Zr, M = Zr, R = SiMe₃; 2-Hf, M = Hf, R = SiMe₃; 3, M = Zr, R = Me) were synthesized by the hydrogenolysis of the half-sandwich tris(trimethylsilylmethyl) complexes [(C₅Me₄R)M(CH₂SiMe₃)₃] (1-Zr, M = Zr, R = SiMe₃; 1-Hf, M = Hf, R = SiMe₃; 1-Zr鈥?/b>, M = Zr, R = Me). X-ray diffraction studies revealed that these hydride clusters possess a tetrahedral M₄ framework which is connected by two 渭₃-H and six 渭₂-H ligands. Such bonding modes have been further clarified by DFT studies. The reaction of 2-Zr with SePPh₃ resulted in oxidation of two of the four Zr(III) ions in 2-Zr to Zr(IV) and reduction of SePPh₃ to Se^{2鈥?/sup>, yielding the selenium-capped hydride cluster [(C₅Me₄SiMe₃)₄Zr₄(渭₃-Se)(渭-H)₈] (4) with release of PPh₃.}