Cea-Olivares R, Gómez-Ortiz L A, García-Montalvo V, Gaviño-Ramírez R L, Hernández-Ortega S
Instituto de Química, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, México D.F. 04510, Mexico.
Inorg Chem. 2000 May 29;39(11):2284-8. doi: 10.1021/ic991318z.
The reaction of nBuSnCl3 and the sodium salt of 2-mercaptoethanol (1:1) in ethanol gave the compound Sn(nBu)(Cl)[(OCH2CH2S)2Sn(nBu)]2 (1). [(nBu)Sn(SCH2CH2O)SCH2CH2OH] (2) was initially isolated from the reaction of 1 with nBuMgCl as a rearrangement product but was also synthesized from nBuSn(O)OH and two molar equivalents of 2-mercaptoethanol. Both compounds were characterized by means of IR, 119Sn, 13C, and 1H NMR, FAB mass spectroscopy, and elemental analyses. The structures were determined by single-crystal X-ray diffraction. 1 crystallizes in the monoclinic Cc space group (a = 18.492(3) A, b = 17.329(2) A, c = 10.787(1) A, beta = 111.88(1) degrees, Z = 4), while 2 crystallizes in the orthorhombic Pbca space group (a = 14.458(2) A, b = 10.393(1) A, c = 16.479(2) A, Z = 8). 1 is a trimetallic Tin(IV) compound in which the central atom is in 6-fold coordination, while the two remaining tin atoms show 5-fold coordination. Both pentacoordinated tin atoms are bonded to a butyl group and to the oxygen and the sulfur atoms from two [OCH2CH2S]2- ligands forming two stannolanes, which are fused with the hexacoordinated tin atom forming a distannoxane system. This arrangement is quite different from previous ladder or staircase structures. NMR data point to maintenance of this structure in solution. 2 consists of [(nBu)Sn(SCH2CH2O)(SCH2CH2OH)] units, which are associated via intermolecular Sn-O interactions building up a dimer. The tin atom forms two "stannolane" units by interaction with [OCH2CH2S]2- and [HOCH2CH2S]- ligands.
正丁基三氯化锡与2-巯基乙醇的钠盐（1:1）在乙醇中反应生成化合物Sn(nBu)(Cl)[(OCH2CH2S)2Sn(nBu)]2（1）。[(nBu)Sn(SCH2CH2O)SCH2CH2OH]（2）最初是从1与正丁基氯化镁的反应中作为重排产物分离得到的，但也可由正丁基氢氧化锡和两摩尔当量的2-巯基乙醇合成。两种化合物均通过红外光谱、119Sn、13C和1H核磁共振、快原子轰击质谱以及元素分析进行表征。其结构通过单晶X射线衍射确定。1结晶于单斜晶系Cc空间群（a = 18.492(3) Å，b = 17.329(2) Å，c = 10.787(1) Å，β = 111.88(1)°，Z = 4），而2结晶于正交晶系Pbca空间群（a = 14.458(2) Å，b = 10.393(1) Å，c = 16.479(2) Å，Z = 8）。1是一种三金属锡（IV）化合物，其中中心原子呈六配位，而其余两个锡原子呈五配位。两个五配位锡原子均与一个丁基以及来自两个[OCH2CH2S]2-配体的氧和硫原子相连，形成两个锡杂环戊烷，它们与六配位锡原子稠合形成一个二锡氧烷体系。这种排列与先前的梯形或阶梯形结构有很大不同。核磁共振数据表明该结构在溶液中得以保持。2由[(nBu)Sn(SCH2CH2O)(SCH2CH2OH)]单元组成，这些单元通过分子间的Sn - O相互作用缔合形成二聚体。锡原子通过与[OCH2CH2S]2-和[HOCH2CH2S]-配体相互作用形成两个“锡杂环戊烷”单元。
