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Abstract
The reactions of n-butyl stannonic acid with(PhO) 2 P(O)H leads to the formation of a hexameric tin cage [{(n-BuSn) 3 (PhO) 3 O} 2 {HPO 3 } 4 ].This reaction involves an in situ P─O bond cleavage and the generation of a [HPO 3 ] 2− ion. A direct reaction of six equivalents of n-BuSnO(OH) acid with six equivalents of C 6 H 5 OH and four equivalents of H 3 PO 3 also leads to the formation of same cage structure. A tetranuclear organooxotin cage[(PhCH 2 ) 2 Sn 2 O(O 2 P(OH)-t-Bu) 4 ] 2 has been assembled by debenzylation involving the reaction of (PhCH 2 ) 2 SnCl 2 ,(PhCH 2 ) 2 SnO·H 2 O or (PhCH 2 ) 3 SnCl with two equivalents of t-BuP(O)OH 2 . A half-cage intermediate [(PhCH 2 ) 2 Sn 2 O(O 2 P(OH)-t-Bu) 4 ] has been detected. New organotin cations of the type [n-Bu 2 Sn(H 2 O) 4 ] 2+[2,5-Me 2 -C 6 H 3 SO 3 ]− 2 and {[n-Bu 2 Sn(H 2 O) 3 LSn(H 2 O) 3 (n-Bu) 2 ] 2+[1,5-(SO 3 ) 2 -C 10 H 6 ] 2−} have been obtained in the reactions of n-Bu 2 SnO or (n-Bu 3 Sn) 3 O 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.