Intramolecular Chalcogen-Tin Interactions in (o-MeE-C6H4)CH2SnPh3-nCln (E = S, O

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• 作者：Teresita Munguia ; Marcela Ló ; pez-Cardoso ; Francisco Cervantes-Lee ; Keith H. Pannell
• 刊名：Inorganic Chemistry
• 出版年：2007
• 出版时间：February 19, 2007
• 年：2007
• 卷：46
• 期：4
• 页码：1305 - 1314
• 全文大小：299K
• 年卷期：v.46,no.4(February 19, 2007)
• ISSN：1520-510X

文摘

Organotin(IV) compounds of the type (o-MeE-C₆H₄)CH₂SnPh_3-nCl_n were synthesized, E = O, n = 0 (1), n = 1(2), n = 2 (3) and E = S, n = 0 (4), n = 1 (5), n = 2 (6). The complexes exhibit significant trigonal bipyramidalpentacoordination at tin as a consequence of intramolecular Sn-O (1-3) and Sn-S (4-6) interactions uponsubstitution of the phenyl groups by chloro groups. The intramolecular Sn-O distances in 1, 2, and 3 are 83%,75%, and 79% of the sum of the van der Waals radii. The equivalent Sn-S values for 4, 5, and 6 are 90%, 73%,and 71%, respectively. The geometry of compound 3 is complicated by intermolecular dimerization via bridgingchlorines creating a distorted octahedral geometry at tin. The related dichloro sulfur compound 6 also exhibits anintermolecular association in the form of Sn-Cl-H hydrogen bonding leading to a polymeric structure in the solidstate. CPMAS ¹¹⁹Sn NMR spectroscopy suggests that the intramolecular Sn-E interactions persist in solution andalso facilitated the discovery of a new crystalline form of 4, 4', that contains a Sn-S distance which is 95% thesum of the van der Waals radii.