Structural analyses of 2-triorganylsilyl- and 2-triorganylstannyl derivatives of 5-alkyl-[1,3,5]-dithiazinanes. Do S center dot center dot center dot Si and S center dot center dot center dot Sn interactions exist?

作者：Colorado Peralta Raul; Guadarrama Perez Carlos; Martinez Chavando Luis A; Carlos Galvez Ruiz Juan; Duarte Hernandez Angelica M; Suarez Moreno Galdina V; Vasquez Badillo Aurora; Sanchez Ruiz Sonia A; Contreras Rosalinda; Flores Parra Angelina^*

来源：Journal of Organometallic Chemistry, 2014, 751: 579-590.

DOI：10.1016/j.jorganchem.2013.07.058

• 2-R3Si-[1,3,5]-dithiazinanes
• 2-R3Sn-[1,3,5]-dithiazinanes
• N-borane adducts
• S center dot center dot center dot Si and S center dot center dot center dot Sn weak interactions
• Conformational analyses

A series of 2 - R-3'E (E = Si or Sn; R' = Me or Ph) derivatives of 5-R-[1,3,5]-dithiazinanes (R = Me, iPr, tBu) are reported, as well as some of their N-BH3 adducts. Structures were determined by Si-29, Sn-119, B-11, C-13 and H-1 NMR and X ray diffraction analyses. Minimum energy conformations were calculated by HF/631++G(d,p) and B3LYP/6-31++G(d,p) methods. Preferred conformations and steric and stereo-electronic interactions are analyzed. In the solid state the ring conformation is a chair with the N-R group in axial and the 2-substituents in equatorial position. The Si or Sn atoms linked to C-2 have short distances to the two sulfur atoms, interpreted as Si center dot center dot center dot S and Sn center dot center dot center dot S stabilizing contacts. The Sn-119 NMR chemical shifts and (1)J(C-13, Sn-119) coupling constants evidenced weak S center dot center dot center dot Sn coordination bonds. Substitution reactions at C2 performed in N-BH3 adducts of 2-lithium-5-methyl-[1,3,5]-dithiazinanes of anchored conformation proceed with retention of C2 configuration.

• 出版日期2014-2-1