Tripodal aminophenolate ligand complexes of aluminum(III), gallium(III), and indium(III) in water

被引:47
作者
Caravan, P [1 ]
Orvig, C [1 ]
机构
[1] UNIV BRITISH COLUMBIA,DEPT CHEM,VANCOUVER,BC V6T 1Z1,CANADA
关键词
D O I
10.1021/ic961222u
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Four water-soluble amine phenols have been prepared: tris(((2-hydroxy-5-sulfobenzyl)amino)ethyl)amine (H(6)TRNS), 1,1,1-tris(((2-hydroxy-5-sulfobenzyl)amino)methyl)ethane (H(6)TAMS), 1,2,3-tris((2-hydroxy-5-sulfobenzyl)amino)propane (H(6)TAPS), and cis,cis-1,3,5-tris((2-hydroxy-5-sulfobenzyl)amino)cyclohexane (H(6)TACS). Complex formation constants have been measured at 25 degrees C (mu = 0.16 M NaCl): log K [M(TRNS)](3-) ([M(HTRNS)](2-)) M = Ga 28.55 (36.90), In 29.3 (34.9); log K [M(TAMS)](3-) ([M(HTAMS)](2-)) M = Al 22.5 (29.3), Ga 31.53, In 28.49; log K [M(TAPS)](3-) ([M(HTAPS)](2-)) M = Al 22.8 (29.0), Ga 31.54 (35.15), In 27.56 (31.93). The order of stability is Ga(III) > In(III) > Al(III) for H(6)TAMS and H(6)TAPS, while far H(6)TRNS it is Ga(III) approximate to In(lII) > Al(III). The solution structures of the complexes have been probed by multinuclear NMR (H-1, C-13, Al-27, Ga-71, In-115) and UV spectroscopic studies, and these solution structures are compared with solid state structures for analogous complexes. The H-1 NMR spectrum in D2O establishes TAPS to be preorganized for metal ion binding. H(6)TACS exists in the wrong conformation for metal ion binding, and this results in slow complexation kinetics and relatively weaker binding.
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页码:236 / 248
页数:13
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