Reaction of Butyltin Hydroxide Oxide with p-Toluenesulfonic Acid: Synthesis, X-ray Crystal Analysis, and Multinuclear NMR Characterization of {(BuSn)12O14(OH)6}(4-CH3C6H4SO3)2

The reaction of butyltin hydroxide oxide, BuSnO(OH), with p -toluenesulfonic acid, 4-CH 3 C 6 H 4 SO 3 H, yields the butyltin oxo cluster {(BuSn) 12 (μ 3 -O) 14 (μ 2 -OH) 6 } 2+ mixed with a soluble ill-defined butyltin oxo polymer, the presence of which was established by solid-state and quantitative solution 119 Sn NMR. The reaction conditions were varied in order to optimize the yield of oxo cluster, which can be quantitatively isolated by crystallization as {(BuSn) 12 O 14 (OH) 6 }(4-CH 3 C 6 H 4 SO 3 ) 2 ·C 4 H 8 O 2 ( 1 ·diox). The structure of the latter compound was determined by X-ray diffraction. 1 ·diox and {(BuSn) 12 O 14 (OH) 6 }(4-CH 3 C 6 H 4 SO 3 ) 2 ( 1 ) were also characterized by solid-state 119 Sn MAS NMR and solution 119 Sn, 1 H, and 13 C NMR. In 1 ·diox, the existence of weak Lewis interactions, taking place in the crystal between five-coordinate tin atoms and dioxane molecules, was evidenced by solid-state 119 Sn NMR. 2D 1 H− 1 H NOESY and ROESY experiments, along with ionic conductivity measurements, have proved that the ionic dissociation between {(BuSn) 12 O 14 (OH) 6 } 2+ and 4-CH 3 C 6 H 4 SO 3 - (PTS - ) does not take place in dichloromethane, while it does in the more polar and dissociating dimethyl sulfoxide. Using the 1 H− 119 Sn J -HMQC NMR technique, the weak 2 J ( 1 H−O− 119 Sn) coupling constant between the μ 2 -OH and the six-coordinate tin nuclei was determined and shown to depend on the solvent.