Inclusion Properties of 1,4-(Triorganostannyl and -silyl)buta-1,3-diynes: Thermal, Structural, and NMR Spectroscopic Aspects

详细信息    查看全文

• 作者：Francis Carré ; Sylvain G. Dutremez ; Christian Gué ; rin ; Bernard J. L. Henner ; Agn&egrave ; s Jolivet ; Vé ; ronique Tomberli ; and Franç ; oise Dahan
• 刊名：Organometallics
• 出版年：1999
• 出版时间：February 15, 1999
• 年：1999
• 卷：18
• 期：4
• 页码：770 - 781
• 全文大小：157K
• 年卷期：v.18,no.4(February 15, 1999)
• ISSN：1520-6041

文摘

The tin-containing diyne Ph₃SnCges/entities/tbd1.gif">CCges/entities/tbd1.gif">CSnPh₃ (4) forms 1:1 host-guest complexes witha large variety of organic molecules. These complexes have been characterized by ¹H NMRspectroscopy, thermogravimetry (TGA), and differential scanning calorimetry (DSC). Weakinteractions between the host and guest molecules are observed with toluene, tetrachloroethane, and p-xylene (the latter gives a 2:1 complex). Strong interactions are found withdichloromethane, chloroform, tetrahydrofuran, and dioxane. An intermediate behavior isobserved with acetone, benzene, and pyridine. Guest-selectivity studies have been carriedout on some of these complexes that confirm the results obtained from the TGA measurements. A single-crystal X-ray diffraction analysis of 4:dioxane shows that it has a trueclathrate (cage) structure with the guest molecule being surrounded by 12 phenyl groupsfrom 6 Ph₃Sn moieties. Inclusion compounds do not form when the length of the spacer isshortened, i.e. with Ph₃SnCges/entities/tbd1.gif">CSnPh₃, or when the SnPh₃ groups of 4 are replaced by SnMe₃moieties. On going from Ph₃SnCges/entities/tbd1.gif">CCges/entities/tbd1.gif">CSnPh₃ to Ph₃Sn(CH₂)₄SnPh₃, i.e. when the rigiddiacetylene fragment is replaced by the flexible butanediyl group, formation of a clathrateis observed only in the case of dioxane. When Ph₂PCges/entities/tbd1.gif">CCges/entities/tbd1.gif">CPPh₂ or Ph₃SiCges/entities/tbd1.gif">CCges/entities/tbd1.gif">CSiPh₃is used as host instead of Ph₃SnCges/entities/tbd1.gif">CCges/entities/tbd1.gif">CSnPh₃, there is no evidence for clathrate formation.However, in the case of Ph₃SiCges/entities/tbd1.gif">CCges/entities/tbd1.gif">CSi*MePhNp (5: Np = 1-naphthyl), a 1:1 clathrate isobtained with dioxane. A single-crystal X-ray diffraction analysis of the 5:dioxane inclusioncompound shows that the guest molecule lies exclusively in channels formed by phenylsubstituents from the Ph₃Si groups. Solid-state ¹³C, ¹¹⁹Sn, and ²⁹Si NMR and X-ray powderdiffraction analyses have been carried out on 4:CHCl₃, 4:dioxane and 5:dioxane prior to andafter removal of the guest molecules, and the results demonstrate the structure-stabilizingability of these molecules. It has been possible to obtain single crystals of 4 with no includedsolvent, and the X-ray crystal structure of this material shows that the organization of thediacetylenic compound is such that it leads to a more compact packing as compared to thatfound in 4:dioxane.