Systematic Structural Coordination Chemistry of p-tert-Butyltetrathiacalix[4]arene: 1. Group 1 Elements and Congeners

A. Bilyk, A.K. Hall, J.M. Harrowfield, M.W. Hosseini, Brian Skelton, Allan White

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108 Citations (Scopus)

Abstract

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.
Original languageEnglish
Pages (from-to)672-686
JournalInorganic Chemistry
Volume40
DOIs
Publication statusPublished - 2001

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