Reaction of butyltin hydroxide oxide with p-toluenesulfonic acid: Synthesis, X-ray crystal analysis, and multinuclear NMR characterization of {(BuSn)(12)O-14(OH)(6)}(4-CH3C6H4SO3)(2)

The reaction of butyltin hydroxide oxide, BuSnO(OH), with p-toluenesulfonic acid, 4-CH3C6H4SO3H, yields the butyltin oxo cluster ((BuSn)(12)(mu(3)-O)( 14)(mu(2)-OH)(6))(2+) mixed with a soluble ill-defined butyltin oxo polymer , the presence of which was established by solid-state and quantitative sol ution Sn-119 NMR. The reaction conditions were varied in order to optimize the yield of oxo cluster, which can be quantitatively isolated by crystalli zation as {(BuSn)(12)O-14(OH)(6)}(4-CH3C6H4SO3)(2). C4H8O2 (1 . diox). The structure of the latter compound was determined by X-ray diffraction. 1 . d iox and {(BuSn)(12)O-14(OH)(6)}(4-CH3C6H4SO3)(2) (1) were also characterize d by solid-state Sn-119 MAS NMR and solution Sn-119, H-1, and C-13 NMR. In 1 . diox, the existence of weak Lewis interactions, taking place in the cry stal between five-coordinate tin atoms and dioxane molecules, was evidenced by solid-state 119Sn NMR. 2D H-1-H-1 NOESY and ROESY experiments, along wi th ionic conductivity measurements, have proved that the ionic dissociation between {(BuSn)(12)O-14(OH)(6)}(2+) and 4-CH3C6H4SO3- (PTS-) does not take place in dichloromethane, while it does in the more polar and dissociating dimethyl sulfoxide. Using the H-1-Sn-119 J-HMQC NMR technique, the weak (2 )J(H-1-O-Sn-119) coupling constant between the mu(2)-OH and the six-coordin ate tin nuclei was determined and shown to depend on the solvent.