Reaction of Butyltin Hydroxide Oxide with p-Toluenesulfonic Acid: Synthesis, X-ray Crystal Analysis, and Multinuclear NMR Characterization of {(BuSn)12O14(OH)6}
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- 作者：Christophe Eychenne-Baron ; Franç ; ois Ribot ; Nathalie Steunou ; Clé ; ment Sanchez ; Franck Fayon ; Monique Biesemans ; José ; C. Martins ; and Rudolph Willem
- 刊名：Organometallics
- 出版年：2000
- 出版时间：May 15, 2000
- 年：2000
- 卷：19
- 期：10
- 页码：1940 - 1949
- 全文大小：139K
- 年卷期：v.19,no.10(May 15, 2000)
- ISSN：1520-6041
文摘
The reaction of butyltin hydroxide oxide, BuSnO(OH), with p-toluenesulfonic acid,4-CH3C6H4SO3H, yields the butyltin oxo cluster {(BuSn)12(
3-O)14(2-OH)6}2+ mixed with asoluble ill-defined butyltin oxo polymer, the presence of which was established by solid-state and quantitative solution 119Sn NMR. The reaction conditions were varied in order tooptimize the yield of oxo cluster, which can be quantitatively isolated by crystallization as{(BuSn)12O14(OH)6}(4-CH3C6H4SO3)2·C4H8O2 (1·diox). The structure of the latter compoundwas determined by X-ray diffraction. 1·diox and {(BuSn)12O14(OH)6}(4-CH3C6H4SO3)2 (1) werealso characterized by solid-state 119Sn MAS NMR and solution 119Sn, 1H, and 13C NMR. In1·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 119Sn NMR.2D 1H-1H NOESY and ROESY experiments, along with ionic conductivity measurements,have proved that the ionic dissociation between {(BuSn)12O14(OH)6}2+ and 4-CH3C6H4SO3-(PTS-) does not take place in dichloromethane, while it does in the more polar anddissociating dimethyl sulfoxide. Using the 1H-119Sn J-HMQC NMR technique, the weak2J(1H-O-119Sn) coupling constant between the 2-OH and the six-coordinate tin nuclei wasdetermined and shown to depend on the solvent.
3-O)14(2-OH)6}2+ mixed with asoluble ill-defined butyltin oxo polymer, the presence of which was established by solid-state and quantitative solution 119Sn NMR. The reaction conditions were varied in order tooptimize the yield of oxo cluster, which can be quantitatively isolated by crystallization as{(BuSn)12O14(OH)6}(4-CH3C6H4SO3)2·C4H8O2 (1·diox). The structure of the latter compoundwas determined by X-ray diffraction. 1·diox and {(BuSn)12O14(OH)6}(4-CH3C6H4SO3)2 (1) werealso characterized by solid-state 119Sn MAS NMR and solution 119Sn, 1H, and 13C NMR. In1·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 119Sn NMR.2D 1H-1H NOESY and ROESY experiments, along with ionic conductivity measurements,have proved that the ionic dissociation between {(BuSn)12O14(OH)6}2+ and 4-CH3C6H4SO3-(PTS-) does not take place in dichloromethane, while it does in the more polar anddissociating dimethyl sulfoxide. Using the 1H-119Sn J-HMQC NMR technique, the weak2J(1H-O-119Sn) coupling constant between the 2-OH and the six-coordinate tin nuclei wasdetermined and shown to depend on the solvent.