Complexes of aluminium, gallium and indium trifluorides with neutral oxygen donor ligands: Synthesis, properties and reactions
Complexes of aluminium, gallium and indium trifluorides with neutral oxygen donor ligands: Synthesis, properties and reactions
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DOI：
10.1016/j.poly.2015.12.032
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发表时间：
2016-02-26
期刊：
影响因子：
2.6
通讯作者：
Reid, Gillian
中科院分区：
文献类型：
--
作者：
Bhalla, Rajiv;Burt, Jennifer;Reid, Gillian
MF3中心点3 H(2)O(M=Al，Ga或In)溶于热的二甲基亚砜(DMSO)，形成[MF3(OH2)(2)(DMSO)]；进一步的DMSO即使在长时间回流后也不被加入。[GaF3(OH2)(2)(DMSO)]的X-射线结构显示了多氟化合物和反式OH2配体。在室温下，[GaF3(OH2)(2)(DMSO)]与Me(3)-Tacn(1，4，7-三甲基-1，4，7-三氮杂环烷)或2，2‘-联吡啶反应，得到[GaF3(Me(3)Tacn)]中心点CHH2O和[GaF3(Bipy)(OH2)]中心点2H(2)O。[MF3(OH2)(2)(DMSO)](M=Al或Ga)在CH2Cl2或MeOH中不与R3PO(R=Me或Ph)反应，而与吡啶-N-氧化物反应，产物为[AlF3(OH2)(2)(PyNO)]和[GaF3(OH2)(2)(PyNO)]中心点pyNO中心点H2O。后者的结构表现为具有多反构型和多顺构型的几何异构体，以及晶格的PYNO和H2O。五甲基二亚乙基三胺(PMDTA)和[GaF3(OH2)(2)(DMSO)]反应生成两性离子[GaF4(PMDTAH)]中心点2H(2)O，其中含有k(2)-PMDTA和‘游离’NMe2基团质子化，以平衡GaF4-单元的电荷。作为次要副产物，得到了含有1，1，4-三甲基哌嗪阳离子的[Me2N(CH2)(2)NMe(CH2)(2)](2)[Ga2F8(OH2)(2)]center点H2O的子集]晶体。阴离子是一种边共享的氟桥联二聚体，配位的水配体排列成反的。从相应的[NMe4]F氯络合物通过氯/氟交换制备膦或硫醚络合物的尝试失败了，卤化物交换伴随着软给体配体的释放。还报道了[Me2NH2][trans-GaF4(OH2)(2)]和[AlCl3(OAsPh3)]的X射线结构。(C)2015年提交人。爱思唯尔有限公司出版。
The MF3 center dot 3H(2)O (M = Al, Ga or In) dissolve in hot dimethylsulfoxide (dmso) to form [MF3(OH2)(2)(dmso)]; further dmso is not incorporated even after prolonged reflux. The X-ray structure of [GaF3(OH2)(2)(dmso)] shows mer fluorides and trans OH2 ligands. The [GaF3(OH2)(2)(dmso)] reacts with Me(3)tacn (1,4,7-trimethyl-1,4,7-triazacyclononane) or 2,2'-bipyridyl to give good yields of [GaF3(Me(3)tacn)]center dot chi H2O and [GaF3(bipy)(OH2)]center dot 2H(2)O at room temperature, previously obtained from GaF3 center dot 3H(2)O by a hydrothermal route. [MF3(OH2)(2)(dmso)] (M = Al or Ga) do not react with R3PO (R = Me or Ph) in CH2Cl2 or meOH, but with pyNO (pyridine-N-oxide), the products were [AlF3(OH2)(2)(PyNO)] and [GaF3(OH2)(2)(pyNO)]center dot pyNO center dot H2O. The structure of the latter shows equal numbers of the geometric isomers with mer-trans and mer-cis geometries, as well as lattice pyNO and H2O. Pentamethyldiethylenetriamine (PMDTA) and [GaF3(OH2)(2)(dmso)] react to produce the zwitterion [GaF4(PMDTAH)]center dot 2H(2)O, which contains k(2)-PMDTA with the 'free' NMe2 group protonated to balance the charge of the GaF4- unit. Crystals of [subset of Me2N(CH2)(2)NMe(CH2)(2)](2)[Ga2F8(OH2)(2)]center dot H2O containing a 1,1,4-trimethylpiperazinium cation, were obtained as a minor by-product. The anion is an edge-shared fluoride-bridged dimer, with the coordinated water ligands arranged anti. Attempts to prepare complexes with phosphine or thioether ligands by Cl/F exchange from the corresponding chloro-complexes with [NMe4]F were unsuccessful, halide exchange being accompanied by liberation of the soft donor ligand. X-ray structures are also reported for [Me2NH2][trans-GaF4(OH2)(2)] and [AlCl3(OAsPh3)]. (C) 2015 The Authors. Published by Elsevier Ltd.