Synthesis, structure and characterization of new stibocanes substituted with dithiophosphate ligands

详细信息	查看全文 | 推荐本文 |

• 作者：Patricia Garc&iacute ; a y Garc&iacute ; a^b ; Patricia Mart&iacute ; nez-Salas^b ; Simó ; n Herná ; ndez-Ortega^a ; Perla Romá ; n-Bravo^b ; Marcela Ló ; pez-Cardoso^b ; Mar&iacute ; a del Carmen Pé ; rez-Redondo^c ; Gabriela Vargas-Pineda^b ; Ave Mar&iacute ; a Cotero-Villegas^c ; Raymundo Cea-Olivares^a ; ^{cea@servidor.unam.mx}
• 关键词：Stibocanes ; Dithiophosphate cyclic ; 1 ; 1-Dithiolates ; Dioxaphosphinane
• 刊名：Polyhedron
• 出版年：2012
• 期刊代码：87_02775387
• 类别：ch
• 出版时间：23 April, 2012
• 卷：37
• 期：1
• 页码：48-53
• 文件大小：774 K

摘要

Four new stibocanes substituted with cyclic dithiophosphate ligands O(CH₂CH₂S)₂SbS₂P(OCH₂)₂CEt₂ (1), O(CH₂CH₂S)₂SbS₂P(OCH₂)₂C(Me)Pr (2), S(CH₂CH₂S)₂SbS₂P(OCH₂)₂CEt₂ (3) and S(CH₂CH₂S)₂SbS₂P(OCH₂)₂C(Me)Pr (4) were prepared from the corresponding chloro oxa- and thia-stibocanes and the sodium salt of the dithiophosphoric acids 5,5-diethyl-(2-mercapto-2-thiono-1,3,2-dioxaphosphinane) and 5-methyl-5-propyl-(2-mercapto-2-thiono-1,3,2-dioxaphosphinane) in ethanol. The compounds obtained were characterized by IR, EI-MS and multinuclear NMR (¹H, ¹³C, ³¹P) spectroscopies. The single-crystal structures of 1 and 2 were determined which show the presence of three types of secondary bonding: i.e. strong Sb- - -O transannular interactions of 2.607(4) and 2.600(4) 脜, respectively, anisobidentate coordination of the ligand (exocyclic chelation) average Sb- - -S distance 3.355 脜 and intermolecular interactions that lead to supramolecular associations. The coordination geometry around antimony atom in both 1 and 2 can be described as 唯 tricapped trigonal bipyramidal AB₄CD₂E. The eight membered ring presents a boat-chair conformation in both compounds and the 1,3,2-dioxaphosphinane ring has the chair conformation, with the stibocane in the axial position.