Homo- and Heteropolynuclear Clusters of Phosphine Triphenolates

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• 作者：Lan-Chang Liang ; Kuan-Wei Chou ; Wei-Jia Su ; Han-Sheng Chen ; Yu-Lin Hsu
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：December 7, 2015
• 年：2015
• 卷：54
• 期：23
• 页码：11526-11534
• 全文大小：583K
• ISSN：1520-510X

文摘

The synthesis and structural characterization of a series of homo- and heteropolynuclear clusters constructed with a potentially tetradentate phosphine triphenolate ligand are presented. Treatment of tris(3,5-di-tert-butyl-2-hydroxyphenyl)phosphine (H₃[O₃P]) with 3 equiv of nBuLi in diethyl ether at 鈭?5 掳C affords hexanuclear Li₆[O₃P]₂(OEt₂)₂ (1) as colorless crystals. In situ lithiation of H₃[O₃P] with 3 equiv of nBuLi in THF at 鈭?5 掳C followed by metathetical reactions with MnCl₂ or NiCl₂(DME) gives crystals of forest green pentanuclear MnLi₄[O₃P]₂(THF)₃ (2) or dark brown tetranuclear Ni₂Li₂[O₃P]₂(THF)₂ (3), respectively. Alkane elimination of ZnR₂ (R = Me, Et) with H₃[O₃P] in THF at 25 掳C generates high yields of colorless crystalline trinuclear Zn₃[O₃P]₂(THF)₂ (4). The cluster structures of 1鈥?b>4 were all determined by single crystal X-ray diffraction studies. These molecules represent the first examples of metal complexes supported by phosphine triphenolate derivatives. The cluster 2 contains a paramagnetic core of high spin Mn(II) (S = 5/2) as indicated by solution and solid state magnetic susceptibility measurements.