Cyclotristannoxane (R2SnO)3 and cyclotristannane (R2Sn)3 systems. Synthesis and crystal structures
Cyclotristannoxane (R2SnO)3 and cyclotristannane (R2Sn)3 systems. Synthesis and crystal structures
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DOI：
10.1021/ja00341a058
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发表时间：
1983-02
影响因子：
15
通讯作者：
S. Masamune;L. Sita;D. Williams
中科院分区：
文献类型：
--
作者：
S. Masamune;L. Sita;D. Williams
我们在此描述了两种化合物的合成和晶体结构：六(2,6-二乙基苯基)环三锡氧烷(1)和六(2,6-二乙基苯基)环三锡烷(2)。后者的环三锡烷体系显然构成了仅由锡原子组成的最小环状骨架1，而化合物1是一种罕见的结晶二有机氧化锡，具有具有四配位锡原子的离散分子结构。 2 二有机锡二卤化物的碱解是制备相应氧化锡的最常见方法，在过去总是导致形成不溶性聚合物，该化合物表现出宽熔程以及表明五配位锡的穆斯堡尔谱。 3 1 和2 的晶体学分析 (1) 四元环和更大的环系早已为人所知。评论请参阅：(a) Gilman, H.；阿特韦尔，WH； Cortledge，F.K.Adv。有机体。化学。 1964, 4, 1.(b) Armitage, D. A.“无机环和笼”；爱德华·阿诺德：伦敦，1972 年；第 4 章。另请参阅以下引用的参考文献：(c) Neumann, W. P. Rev. 硅、锗、锡、铅化合物。 1978, 3, 51.(d) 石川，M.； Kumada，M.同上。 1979, 4, 7.(e) Neumann, W. P. Nachr。化学。技术。实验室。 1982, 30, 191.(2) 假定溶液中以三聚体 (z-Bu2SnO) 3 形式存在的二叔丁基氧化锡是唯一具有四配位锡原子的二有机氧化锡 [(a) Chu, C. K.;默里，J.D.J.化学。苏克。 1971 年，360]。该化合物的晶体结构参见：(b) Puff, H.；西弗斯，R.；齐默，R.；舒，W.安吉。化学，国际。埃德。英语。 1981, 20, 591.(3) 这种行为与硅和锗的类似氧化物的行为形成鲜明对比，它们分别容易形成环三硅氧烷和环三甲氧烷。参见参考文献 lb 和以下内容：Metlesics，W.；蔡司，H.J.Am。化学。苏克。 1960, 82, 3324。
We describe herein the synthesis and crystal structures of two compounds, hexakis (2, 6-diethylphenyl) cyclotristannoxane (1) and hexakis (2, 6-diethylphenyl) cyclotristannane (2). The latter cy-clotristannane system obviously constitutes the smallest cyclic framework made exclusively of tin atoms1, while compound 1 is a rare crystalline diorgano tin oxide that possesses a discrete molecular structure with tetracoordinate tin atoms. 2 The alkaline hydrolysis of diorgano tin dihalides, the most common method of preparing the corresponding tin oxide, always in the past led to the formation of insoluble polymeric compounds exhibiting wide melting ranges as well as Mossbauer spectra indicative of pen-tacoordinate tin. 3 Crystallographic analyses of both 1 and 2 (1) Four-membered and larger ring systems have long been known. For reviews, see:(a) Gilman, H.; Atwell, WH; Cortledge, F. K. Adv. Orga-nomet. Chem. 1964, 4, 1.(b) Armitage, D. A.“Inorganic Rings and Cages”; Edward Arnold: London, 1972; Chapter 4. Also see references quoted in:(c) Neumann, W. P. Rev. Silicon, Germanium, Tin, Lead Compd. 1978, 3, 51.(d) Ishikawa, M.; Kumada, M. Ibid. 1979, 4, 7.(e) Neumann, W. P. Nachr. Chem. Tech. Lab. 1982, 30, 191.(2) Di-zerz-butyltin oxide postulated to exist as the trimer (z-Bu2SnO) 3 in solution is the only other diorgano tin oxide with tetracoordinate tin atoms [(a) Chu, C. K.; Murray, J. D. J. Chem. Soc. A 1971, 360]. For the crystal structure of this compound, see:(b) Puff, H.; Sievers, R.; Zimmer, R.; Schuh, W. Angew. Chem., Int. Ed. Engl. 1981, 20, 591.(3) This behavior is in sharp contrast with thatof the analogous oxides of silicon and germanium, which readily form cyclotrisiloxanes and cyclotrigermoxane, respectively. See ref lb and the following: Metlesics, W.; Zeiss, H. J. Am. Chem. Soc. 1960, 82, 3324.