Systematic structural coordination chemistry of p-tert-butyltetrathiacalix[4]arene:: 1.: Group 1 elements and congeners

被引:107
作者
Bilyk, A
Hall, AK
Harrowfield, JM [1 ]
Hosseini, MW
Skelton, BW
White, AH
机构
[1] Univ Western Australia, Special Res Ctr Adv Mineral & Mat Proc, Nedlands, WA 6907, Australia
[2] Univ Western Australia, Dept Chem, Nedlands, WA 6907, Australia
[3] Univ Strasbourg 1, Inst Le Bel, Chim Coordinat Organ Lab, F-67000 Strasbourg, France
关键词
D O I
10.1021/ic001008c
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Determinations of the crystal structures of complexes of the alkali metal ions with, in the case of Li, the dianion and, in the cases Na-Cs, the monoanion of p-tert-butyltetrathiacalix[4]arene have shown that both the sulfur atoms which form part of the macrocyclic ring, as well as the pendent phenolic/phenoxide oxygen donor atoms, are involved in coordination to these metals. Although the Li and Na complex structures are similar to these of the corresponding complexes of p-tert-butylcalix[4]arene, there is no similarity in the structures of the Cs complexes, with the present structure showing no evidence of polyhapto Cs+-pi interactions. Instead, the complex crystallizes as a ligand-bridged (S-, O-donor) aggregate of three Cs ions, solvent molecules, and four calixarenes, somewhat like the Rb complex, though here four Rb ions are present, and higher in aggregation than the K+ complex, where two K+ ions are sandwiched between two calixarene moieties. The triethylammonium complex of the thiacalixarene monoanion, though formally analogous in that it involves a monocation. has a simpler structure than any of the alkali metal derivatives, based formally on proton coordination (H-bonding). However, interestingly, it can be isolated in both solvated (dmf, dmso) and unsolvated forms, as indeed can the "free", p-tert-butyltetrathiacalix[4]arene ligand itself.
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页码:672 / 686
页数:15
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