COMPLEXATION CHEMISTRY OF BISMUTH(III) HALIDES WITH CROWN ETHERS AND POLYETHYLENE GLYCOLS - STRUCTURAL MANIFESTATIONS OF A STEREOCHEMICALLY ACTIVE LONE PAIR

被引:140
作者
ROGERS, RD
BOND, AH
AGUINAGA, S
REYES, A
机构
[1] Department of Chemistry, Northern Illinois University, DeKalb
关键词
D O I
10.1021/ja00034a032
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The reactions of BiCl3 or BiBr3 in 3:1 CH3CN:CH3OH with 12-crown-4, 15-crown-5, benzo-15-crown-5, tetraethylene glycol (EO4), or pentaethylene glycol (EO5) produce complexes consisting of the neutral, pyramidal BiX3 unit coordinated very weakly to the oxygen donors of the ligands. The 12-crown-4 complexes are seven-coordinate while all of the remaining complexes are 8-coordinate including two pentadentate EO5 complexes. The polyethylene glycol (PEG) ligands closely mimic the conformations of analogous crown ethers. When 18-crown-6 is used in these reactions, two completely different 8-coordinate complexes are isolated: the tridentate [BiCl3(MeOH)(18-crown-6)] and the ionic [BiBr2(18-crown-6)][BiBr4]. Reaction of BiBr3 with hexaethylene glycol (EO6) produces an 8-coordinate complex with a hexadentate EO6 ligand analogous to that obtained with 18-crown-6, [BiBr2(EO6)][BiBr4]. The use of BiI3 results in the formation of polymeric anions which hinder solubility and the isolation of pure complexes. The only completely characterized product was formed by reaction with EO5, [BiI2(EO5)][Bi2I7].2MeOH. (The glycol mimics 18-crown-6.) Structural analysis of the products appears to support the idea of a stereochemically active lone pair with several directed secondary interactions around the lone pair site. The strong influence of the pyramidal BiX3 unit and very long Bi-O contacts around locations where an active lone pair would be assumed to reside are taken as evidence of lone pair activity. The structurally characterized complexes include [BiBr3(12-crown-4)] (an incomplete characterization), [BiX3(15-crown-5)] (X = Cl, Br), [BiX3(benzo-15-crown-5)] (X = Cl, Br), [BiCl3(MeOH)(18-crown-6)], [BiBr2(18-crown-6)][BiBr4], [BiX3(EO4)] (X = Cl, Br), [BiCl3(EO5)] (form A), [BiCl3(EO5)] (form B), [BiI2(EO5)][Bi2I7].2MeOH, and [BiBr2(EO6)][BiBr4].
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页码:2967 / 2977
页数:11
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