Schulte M, Schürmann M, Jurkschat K
Lehrstuhl für Anorganische Chemie II Fachbereich Chemie, Universität Dortmund, Germany.
Chemistry. 2001 Jan 19;7(2):347-55. doi: 10.1002/1521-3765(20010119)7:2<347::aid-chem347>3.0.co;2-e.
Acid-catalysed hydrolysis of [CH2[(Sn(Ph2)CH2Si(OiPr)Me2]2] followed by subsequent reaction with mercuric chloride in acetone afforded the novel silicon- and tin-containing eight-membered ring [cyclo-CH2[Sn(Cl2)CH2Si(Me2)]2O] in good yield, the crystal structure of which is reported. 119Sn NMR and X-ray studies indicate that [cyclo-CH2[Sn(Cl2)CH2Si(Me2)]2O] acts as a bidentate Lewis acid towards chloride ions exclusively forming the 1:1 complex [(Ph3P)2N]+[cyclo-CH2[Sn(Cl2)CH2Si(Me2)]2OCl]- upon addition of [(Ph3P)2N]+Cl- . Also reported are the synthesis and structure of [K(dibenzo[18]crown-6)]+[cyclo-CH2(Sn(Cl2)CH2Si(Me2)]2OF]-, the first completely characterised organostannate with a C2SnCl2F- substituent pattern. No ring-opening polymerisation could be achieved for [cyclo-CH2[Sn(Cl2)CH2Si(Me2)]2O] or for its perphenylated derivative [cyclo-CH2[Sn(Ph2)CH2Si(Me2)]2O]. The reaction of [cyclo-CH2[Sn(Cl2)CH2Si(Me2)]2O] with Me3O+BF4- gave the tin-containing fluorosilane [CH2[Sn(Cl2)CH2Si(F)Me2]2], in which the Si-F bond is activated by intermolecular Si-F...Sn interactions in the solid state.
[CH2[(Sn(Ph2)CH2Si(OiPr)Me2]2]经酸催化水解，随后在丙酮中与氯化汞反应，以良好产率得到了新型含硅和锡的八元环[环-CH2[Sn(Cl2)CH2Si(Me2)]2O]，并报道了其晶体结构。119Sn NMR和X射线研究表明，[环-CH2[Sn(Cl2)CH2Si(Me2)]2O]作为双齿路易斯酸与氯离子作用，在加入[(Ph3P)2N]+Cl-后仅形成1:1配合物[(Ph3P)2N]+[环-CH2[Sn(Cl2)CH2Si(Me2)]2OCl]-。还报道了[K(二苯并[18]冠-6)]+[环-CH2(Sn(Cl2)CH2Si(Me2)]2OF]-的合成与结构，它是首个具有C2SnCl2F-取代模式且完全表征的有机锡酸盐。[环-CH2[Sn(Cl2)CH2Si(Me2)]2O]及其全苯基化衍生物[环-CH2[Sn(Ph2)CH2Si(Me2)]2O]均无法实现开环聚合。[环-CH2[Sn(Cl2)CH2Si(Me2)]2O]与Me3O+BF4-反应生成了含锡氟硅烷[CH2[Sn(Cl2)CH2Si(F)Me2]2]，其中Si-F键在固态中通过分子间Si-F...Sn相互作用而被活化。
