Department of Chemistry, Indian Institute of Technology, Hauz Khas, New Delhi, India.
Dalton Trans. 2013 Nov 28;42(44):15591-8. doi: 10.1039/c3dt52178h.
A one-pot reaction between di-n-butyl/diethyl/dimethyltin dichloride and dimethylphosphite (MeO)2P(O)H in a solvent free medium (120 °C, 18 h) proceeds smoothly to yield the corresponding diorganotinbis(O-methylphosphite)s, [R2Sn(OP(O)(OMe)H)2]n [R = n-Bu (1), Et (2), Me (3)]. The identity of 1-3 has been established by IR, multinuclear ((1)H, (13)C, (31)P, (119)Sn) NMR, powder X-ray diffraction (PXRD) and X-ray crystallography. The coordination framework in each case adopts a one-dimensional structural motif comprising an infinite array of eight-membered [Sn-O-P-O]2 cyclic rings, with the phosphite ligands acting in a bridging bidentate mode. The structures are extended to two- (for 1) and three-dimensional (for 2, 3) assemblies by virtue of C-H···O hydrogen bonding interactions. The stability and bulk properties of 1-3 have been investigated upon exposure to humid laboratory conditions using (1)H NMR, PXRD and SEM studies. The results conform to a unique chemical modification of 1-3 involving selective de-esterification of P-OMe bonds and the formation of corresponding diorganotinbis(phosphite)s, [R2Sn(OP(O)(OH)H)2]n (1a-3a), as insoluble solids. The results obtained from impedance studies (σ = 10(-4)-10(-6) S cm(-1); E(a) = 0.33-0.42 eV) reveal potential application of 1a-3a as proton conducting materials.
在无溶剂介质中（120°C，18 小时），二丁基/二乙基/二甲基二氯化锡与亚磷酸二甲酯（MeO）2P（O）H 之间的一锅反应顺利进行，生成相应的二有机锡双（O-甲基膦酸酯），[R2Sn（OP（O）（OMe）H）2]n [R = n-Bu（1），Et（2），Me（3）]。通过红外光谱、多核（1H、13C、31P、119Sn）NMR、粉末 X 射线衍射（PXRD）和 X 射线晶体学确定了 1-3 的身份。在每种情况下，配位骨架均采用一维结构基元，包括无限的八元[Sn-O-P-O]2 环状结构阵列，其中膦酸酯配体以桥联双齿模式存在。通过 C-H···O 氢键相互作用，结构扩展为二（对于 1）和三（对于 2、3）组装体。使用 1H NMR、PXRD 和 SEM 研究在暴露于潮湿的实验室条件下研究了 1-3 的稳定性和体积性质。结果与涉及 P-OMe 键的选择性脱酯化和相应的二有机锡双（膦酸酯），[R2Sn（OP（O）（OH）H）2]n（1a-3a）的形成一致，作为不溶性固体。阻抗研究（σ=10（-4）-10（-6）S cm（-1）；E（a）=0.33-0.42eV）的结果表明 1a-3a 作为质子传导材料具有潜在的应用。
