Hydrothermal synthesis of Group 13 metal trifluoride complexes with neutral N-donor ligands
Hydrothermal synthesis of Group 13 metal trifluoride complexes with neutral N-donor ligands
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DOI：
10.1039/c5dt01120e
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发表时间：
2015-01-01
影响因子：
4
通讯作者：
Zhang, Wenjian
中科院分区：
文献类型：
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作者：
Bhalla, Rajiv;Levason, William;Zhang, Wenjian
水合第13族氟化物MF3中心点3H(2)O（M = Al、Ga或In）与2,2':6',2''-三联吡啶、2,2'-联吡啶或1,10-菲咯啉在水热条件下（180℃/15小时）反应产生高产率的配合物[MF3(terpy)]中心点3H(2)O、[MF3(bipy)(OH2)]中心点2H(2)O和[MF3(phen)(OH2)]。 [M'F-3(terpy)]中心点 3H(2)O (M' = Al 或 Ga)、[M'F-3(bipy)(OH2)]中心点 2H(2)O 和 [GaF3(phen)(OH2)] 的 X 射线晶体结构表明，它们都在具有三氟化物配位的金属处含有扭曲的八面体几何结构。广泛的氢键（F中心点中心点H-OH）连接分子。通过微量分析、IR、H-1、F-19{H-1} 和 Al-27 NMR 光谱进一步表征了配合物。相反，三氟化物与无环三胺 N,N,N',N',N'''-五甲基二亚乙基三胺在类似的水热条件下反应，导致三胺裂解并闭环，形成 1,1,4-三甲基哌嗪鎓阳离子，[Me2N-(CH2)(2)NMe-(CH2)(2)](+) 的子集，与氟代金属阴离子，并且通过[Me2N(CH2)(2)NMe-(CH2)(2)](2)[Al2F8(OH2)(2)]中心点2H(2)O的X射线分析证实。强氢键合的[GaF3(terpy)]中心点3H(2)O也通过Cl/F交换从[GaCl3(terpy)]和[NBu4]F或[K(2,2,2-crypt)]F获得。[NH4][PF6]和[GaF3(terpy)]中心点3H(2)O的混合物从水溶液中结晶产生边缘桥接的阳离子络合物， [{Ga(terpy) F}(2)-(mu-F)(2)][PF6](2)。空间更大的 [GaCl3(Bu-t(3)-terpy)] (Bu-t(3)-terpy = 4,4' 4 ''-tris-Bu-t-2,2':6',2 ''-terpyridyl) 的合成和含有三角双锥体阳离子的 [GaCl2(Bu-t(3)-terpy)][GaCl4] 的晶体结构也被确定报道称。
The reactions of the hydrated Group 13 fluorides, MF3 center dot 3H(2)O (M = Al, Ga or In) with 2,2':6',2 ''-terpyridyl, 2,2'-bipyridyl or 1,10-phenanthroline under hydrothermal conditions (180 degrees C/15 h) produced high yields of the complexes [MF3(terpy)]center dot 3H(2)O, [MF3(bipy)(OH2)]center dot 2H(2)O and [MF3(phen)(OH2)]. X-Ray crystal structures of [M'F-3(terpy)]center dot 3H(2)O (M' = Al or Ga), [M'F-3(bipy)(OH2)]center dot 2H(2)O and [GaF3(phen)(OH2)] show that all of them contain distorted octahedral geometries at the metal with mer-trifluoride coordination. Extensive H-bonding (F center dot center dot center dot H-OH) links the molecules. The complexes have been further characterised by microanalysis, IR, H-1, F-19{H-1} and Al-27 NMR spectroscopy. In contrast, reactions of the trifluorides with the acyclic triamine, N,N,N',N',N '''-pentamethyldiethylenetriamine, under similar hydrothermal conditions results in cleavage of the triamine and ring-closure to form the 1,1,4-trimethylpiperazinium cation, [subset of Me2N-(CH2)(2)NMe-(CH2)(2)](+), with fluorometallate anions, and confirmed by X-ray analysis of [subset of Me2N(CH2)(2)NMe-(CH2)(2)](2)[Al2F8(OH2)(2)]center dot 2H(2)O. The strongly H-bonded [GaF3(terpy)]center dot 3H(2)O was also obtained by Cl/F exchange from [GaCl3(terpy)] and [NBu4] F or [K(2,2,2-crypt)] F. Crystallisation of a mixture of [NH4][PF6] and [GaF3(terpy)]center dot 3H(2)O from aqueous solution produced the edge-bridged cationic complex, [{Ga(terpy) F}(2)-(mu-F)(2)][PF6](2). The synthesis of the more sterically bulky [GaCl3(Bu-t(3)-terpy)] (Bu-t(3)-terpy = 4,4' 4 ''-tris-Bu-t-2,2':6',2 ''-terpyridyl) and the crystal structure of [GaCl2(Bu-t(3)-terpy)][GaCl4], which contains a trigonal bipyramidal cation, are also reported.