Synthesis and structural study of bis-, tris- and tetra-[1,3,5]-dithiazinanyl silanes and stannanes

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• 作者：Pedro Montes-Tolentino ; Ra煤l Colorado-Peralta ; Luis A. Mart铆nez-Chav ; o ; Edgar Mijangos ; Ang茅lica M. Duarte-Hern谩ndez ; Galdina V. Su谩rez-Moreno ; Rosalinda Contreras ; Angelina Flores-Parra
• 关键词：Bis- ; tris- and tetra-([1 ; 3 ; 5]-dithiazinan-2-yl)silanes ; Bis- ; tris- and tetra-([1 ; 3 ; 5]-dithiazinan-2-yl)stannanes ; Conformational study ; S鈰疭i and S鈰疭n interactions
• 刊名：Journal of Organometallic Chemistry
• 出版年：1 February, 2014
• 年：2014
• 卷：751
• 期：Complete
• 页码：591-603
• 全文大小：1932 K

文摘

The synthesis and structural study of 23 new bis-, tris-, tetra-(dithiazinan-2-yl)silanes and stannanes is reported. The compounds were obtained by reaction of 5-alkyl-[1,3,5]-dithiazinanes (alkyl聽=聽Me, ⁱPr, ^tBu) with ^tBuLi followed by addition of R鈥?sub>nSiCl_4鈭?em>n or R鈥?sub>nSnCl_4鈭?em>n (n聽=聽0-2, R鈥猜?聽Me and Ph) in THF. Structures were determined by ¹H, ¹³C, ²⁹Si or ¹¹⁹Sn NMR, mass spectrometry and X-ray diffraction analyses. Conformation of compounds in the solid state is discussed. The silanyl and stannanyl groups are in equatorial position in bis and tris-dithiazinanyl compounds in solution. The X-ray diffraction of tetra-(N-isopropyl-dithiazinan-2-yl)stannane showed that the tin atom is bound to two dithiazinanyl groups by equatorial bonds and to other two by axial bonds. Atomic distances indicate sulfur-silicon and sulfur-tin short contacts. NMR data, in particular ²⁹Si and ¹¹⁹SN chemical shifts and ¹J(¹³C, ¹¹⁹Sn) coupling constants, indicate the presence of weak S鈰疭i and S鈰疭n interactions in the compounds. Ab-initio calculations were performed for (eq,eq,eq,eq), (ax,ax,ax,ax) and (eq,eq,ax,ax) conformers in order to find the most stable structures in tetra-(5-methyl-[1,3,5]-dithiazinan-2-yl)silane and tetra-(5-methyl-[1,3,5]-dithiazinan-2-yl)stannane.