Systematic Structural Coordination Chemistry ofp‐tert‐Butyltetrathiacalix[4]arene: Main Group Metal Complexes Other Than Those of Group 1

Abstract

AbstractIn extension of previous work involving structural characterisation of complex salts formed between main group 1 metal ions andp‐tert‐butyltetrathiacalixarene, LH4, the present study encompasses complexes with a wider array of main group 2, 13, 14 metal ions. For group 2, single‐crystal X‐ray structural characterisation of Ca(LH3)2·3dmf (1a), {Ca(LH2)·3dmf}2(1b), Ba(LH3)2·6dmf (2a) and BaCO3·3Ba(LH3)2·3H2O·3CH3CN·12.25CH2Cl2(2b) provides models for various coordination units. For group 13, this applies to {Ga(OH)(LH2)·3.5dmf}2(3), {In(LH)·4EtOH·2CH2Cl2}2(4a) and {In(OH)(LH2)·3CH2Cl2}4(4b), and for group 14, to OPb4(LH)2·6dmf·dmso·2H2O (5). Overall, these define mononuclear (1a,2a), binuclear (1b,3,4b) and tetranuclear (2b,4b,5) species. The calixarene cavities frequently include solvent molecules, though this capacity is clearly influenced by the nature of the bound metal ion(s) and their binding, as well as the associated impact on the conformation of the calixarene ligand(s).