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)₃O₂{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 H₃PO₃ also leads to the formation of same cage structure. A tetranuclear organooxotin cage[(PhCH₂)₂Sn₂O(O₂P(OH)-t-Bu)₄]₂ has been assembled by debenzylation involving the reaction of (PhCH₂)₂SnCl₂,(PhCH₂)₂SnO·H₂O 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(H₂O)₄]²⁺[2,5-Me₂-C₆H₃SO₃]^-₂ and [n-Bu₂Sn(H₂O)₃LSn(H₂O)₃(n-Bu)₂]²⁺[1,5-(SO₃)_2-C₁₀H₆]^2- have been obtained in the reactions of n-Bu₂SnO or (n-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.