Gallium(III) halide complexes with phosphines, arsines and phosphine oxides - a comparative study

被引:30
作者
Cheng, Fei [1 ]
Codgbrook, Hannah L. [1 ]
Hector, Andrew L. [1 ]
Levason, William [1 ]
Reid, Gillian [1 ]
Webster, Michael [1 ]
Zhang, Wenjian [1 ]
机构
[1] Univ Southampton, Sch Chem, Southampton SO17 1BJ, Hants, England
关键词
gallium; phosphine oxide; phosphine; phosphonium; NMR spectroscopy;
D O I
10.1016/j.poly.2007.05.008
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The phosphine oxide complexes [GaX3(Me3PO)] and [(GaX3)(2) {mu-o-C6H4(CH2P(O)Ph-2)(2)}] have been prepared and characterised by microanalysis, IR and multinuclear NMR (H-1, C-13{H-1}, P-31{H-1} and Ga-71) spectroscopy. The structures of [GaCl3(Me2PO)], [(GaBr3)(2){mu-o-C6H4(CH2P(O)Ph-2)(2))] and of the ionic product [GaI2(Me3PO)(2)][GaI4] have been determined and show that the Lewis acidity of the gallium halides towards phosphinoyl ligands diminishes as the halogen becomes heavier. The [GaX3(Ph3E)] (X = Cl, Br or I; E = P or As) and [(GaX3)(2)] {mu-o-C6H4(CH2PPh2)(2)1}] (X = Br or I) have been prepared and their structural and spectroscopic properties compared with those of the phosphinoyl complexes. The results, and competitive solution NMR studies, show that Ga(III) binds the hard R3PO in preference to the softer phosphine or arsine ligands. Hydrolysis of gallium(III) phosphines is shown to lead to [R3PH][GaX4], but in contrast to some other p-block halides, GaX3 do not promote air-oxidation of R3P to R3PO, (C) 2007 Elsevier Ltd. All rights reserved.
引用
收藏
页码:4147 / 4155
页数:9
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