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Systematic Structural Coordination Chemistry of p‐tert ‐Butyltetrathiacalix[4]arene: Further Complexes of Transition‐Metal Ions
Author(s) -
Bilyk Alexander,
Dunlop John W.,
Fuller Rebecca O.,
Hall Annegret K.,
Harrowfield Jack M.,
Hosseini M. Wais,
Koutsantonis George A.,
Murray Ian W.,
Skelton Brian W.,
Stamps Robert L.,
White Allan H.
Publication year - 2010
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200901071
Subject(s) - chemistry , heteronuclear molecule , crystallography , nickel , deprotonation , transition metal , stereochemistry , metal , crystal structure , metal ions in aqueous solution , ion , nuclear magnetic resonance spectroscopy , catalysis , organic chemistry
In extension of earlier work on complexes of p ‐ tert ‐butyltetrathiacalix[4]arene, LH 4 , with late transition‐metal M II species, we report studies of complexes modelled on the basis of single‐crystal X‐ray studies as derivatives of V V , W VI , Mn II , Fe III , Ni II , Cu II and Pd II , the last as a trio of heteronuclear species also involving Ca II . In complexes [VO(OH)(LH 2 ) · 2.5dmf · 2H 2 O] (×2) ( 1 ), Cl 2 W(L) · 3.5C 6 H 6 ( 2 ) and [Mn(LH 2 ) · 3.5CH 2 Cl 2 ] (×2) ( 3 ) included dmf is found only in the partially deprotonated calixarene cavities of 1 and 3 . In oligonuclear OFe 3 (HCO 2 )(LH) 2 · 2H 2 O · 6dmf ( 4 ) and 2Cuac 2 · Cu 2 (L) · dmf · 4.5CH 2 Cl 2 ( 6 ) (ac = acetate) included dmf is found in both. Ni II provides several species, including 5a , binuclear (Et 3 NH)Ni 2 (LH)(LH 2 ) · 2dmf · 2Me 2 CO · H 2 O, 5b , a remarkable hexanuclear (binuclear + tetranuclear) aggregate, Ni 6 (L)(LH) 2 (LH 2 ) · 4MeCN · 6H 2 O, and 5c , an even more remarkable Ni 32 aggregate modelled as (centrosymmetric) Ni 32 (OH) 40 (L) 6 · 8dmso · 10dmf, in which there are two sets of nickel atoms, one disposed at the corners of a cube (Ni 8 ), the other (Ni 24 ) at the vertices of a cuboctahedron (the Ni 8 vertices at the centres of the hexagonal faces); the hydroxy groups comprise two sets: one, (OH) 24 , disposed outside the spheroidal shell of nickel atoms, the other, (OH) 16 , disordered within, the thiacalixarene ligands L 6 being disposed about the axes of the octahedron. Heteronuclear species have been found as Ca II /Pd II combinations CaPd 2 (LH) 2 · 1.5CH 2 Cl 2 ( 7a ), CaPd(LH 2 ) · 3dmso · H 2 O · 4.5MeCN ( 7b ), Ca 2 Pd(LH) 2 · 3.5dmso · 1.5H 2 O · 4MeCN ( 7c ), all with included solvent.