Reaction of n-butyltin dihydroxy chloride with carboxylic and phosphinic acids: Crystal structures of the ladder [{Sn(n-Bu)(O2CCHPh2)}(3)Cl2O2](2) and the unsolvated cluster [{Sn(n-Bu)(O2PPh2)Cl-2}{Sn(n-Bu)(O2PPh2)(2)(OH)}](2)
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The reaction of n-butyltin dihydroxy chloride Sn(n-Bu)(OH) 2Cl (1) with carboxylic and phosphorus based acids has been investigated. Treatment of 1 with diphenylacetic acid affords the ladder [{Sn(n-Bu)(O 2CCHPh 2)} 3Cl 2O 2]2 (2), which upon treatment with AgO 2CMe or triethylamine/water, leads to the prismane [{Sn(n-Bu)(O)(O 2CCHPh 2)] 6 (3). Compound 1 reacts with dicyclooctyl phosphinic acid to afford the mixed nuclear cluster [{Sn(n-Bu)(OH)(O 2P(C 8H 15) 2)} 3O] +[{Sn(n-Bu)Cl 2(O 2P(C 8H 15) 2)} 2(OH)] - (4). From the reaction of 1 with half or one mole equivalent each of t-BuP(O)(OH) 2 and Ph 2POOH in toluene, the unsolvated extended cluster [{Sn(n-Bu)(O 2PPh 2)Cl 2}{Sn(n-Bu)(O 2PPh 2) 2(OH)}] 2 (6) is directly isolated, suggesting the preferential formation of this skeleton. Compound 6 upon hydrolysis in the presence of triethylamine gives the known O-capped cluster, [{Sn(n-Bu)(OH)(O 2PPh 2} 3O] + [O 2PPh 2] - (7). Whereas 2 has a hexanuclear Sn 6O 4 skeleton with three different tins, 6 has an extended tetranuclear [Sn 2(OH)] 2 stannoxane framework. The major structural difference between 2 and other known ladder structures is the presence of a five coordinated terminal tin in 2. Comparison of the stannoxane skeleton in 2 and 6 with other known tin cages is also described.
