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Systematic Structural Coordination Chemistry of p-tert-Butyltetrathiacalix[4]arene: 1. Group 1 Elements and Congeners
journal contribution
posted on 2001-01-13, 00:00 authored by Alexander Bilyk, Annegret K. Hall, Jack M. Harrowfield, M. Wais Hosseini, Brian W. Skelton, Allan H. WhiteDeterminations 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 those 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+−π 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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proton coordinationunsolvated formscalixarene moietiesCs complexestertthiacalixarene monoanionCs ionsmacrocyclic ringpolyhapto CsCongeners DeterminationsbutyltetrathiacalixRb ionsNaSystematic Structural Coordination Chemistryalkali metal derivativesform partLicrystal structuresalkali metal ionssulfur atoms
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