Organostannoxane motifs in cages and supramolecular architectures

Abstract

The reactions of n-butyl stannonic acid with (PhO)2P(O)H leads to the formation of a hexameric tin cage [{(n-BuSn)3(PhO) 3O}2{HPO3}4]. This reaction involves an in situ P-O bond cleavage and the generation of a [HPO3] 2- ion. A direct reaction of six equivalents of n-BuSnO(OH) acid with six equivalents of C6H5OH and four equivalents of H 3PO3 also leads to the formation of same cage structure. A tetranuclear organooxotin cage [(PhCH2)2Sn 2O(O2P(OH)-t-Bu)4]2 has been assembled by debenzylation involving the reaction of (PhCH2) 2SnCl2, (PhCH2)2SnO·H 2O or (PhCH2)3SnCl with two equivalents of t-BuP(O)OH2. A half-cage intermediate [(PhCH2) 2Sn2O(O2P(OH)-t-Bu)4] has been detected. New organotin cations of the type [n-Bu2Sn(H 2O)4]2+[2,5-Me2-C6H 3SO3]2- and {[n-Bu 2Sn(H2O)3LSn(H2O) 3(n-Bu)2]2+[1,5-(SO3) 2-C10H6]2-} have been obtained in the reactions of Yi-Bu2SnO or (Ti-Bu3Sn)3O with 2,5-dimethyl sulfonic acid and 1,5-naphthalene disulfonic acid respectively. These organotin cations form interesting supramolecular structures in the solid state as a result of O-H⋯O hydrogen bonding.