%0 Journal Article
%A Bilyk, Alexander
%A Hall, Annegret K.
%A Harrowfield, Jack M.
%A Hosseini, M. Wais
%A Skelton, Brian W.
%A White, Allan H.
%D 2001
%T Systematic Structural Coordination Chemistry of p-tert-Butyltetrathiacalix[4]arene:
1. Group 1 Elements and Congeners
%U https://acs.figshare.com/articles/journal_contribution/Systematic_Structural_Coordination_Chemistry_of_i_p_i_-_i_tert_i_-Butyltetrathiacalix_4_arene_1_Group_1_Elements_and_Congeners/3601098
%R 10.1021/ic001008c.s002
%2 https://ndownloader.figshare.com/files/5689059
%K proton coordination
%K unsolvated forms
%K calixarene moieties
%K Cs complexes
%K tert
%K thiacalixarene monoanion
%K Cs ions
%K macrocyclic ring
%K polyhapto Cs
%K Congeners Determinations
%K butyltetrathiacalix
%K Rb ions
%K Na
%K Systematic Structural Coordination Chemistry
%K alkali metal derivatives
%K form part
%K Li
%K crystal structures
%K alkali metal ions
%K sulfur atoms
%X 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 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.
%I ACS Publications