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[ cyclo ‐CH 2 {Sn(Cl 2 )CH 2 Si(Me 2 )} 2 O]: Synthesis and Complexation Behaviour of a Novel, Cyclic, Bidentate Lewis Acid and Its Conversion into a Tin‐Containing Fluorosilane with Intermolecular Si−F⋅⋅⋅Sn Bridges
Author(s) -
Schulte Marcus,
Schürmann Markus,
Jurkschat Klaus
Publication year - 2001
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20010119)7:2<347::aid-chem347>3.0.co;2-e
Subject(s) - chemistry , tin , denticity , substituent , lewis acids and bases , ring (chemistry) , derivative (finance) , yield (engineering) , chloride , medicinal chemistry , intermolecular force , stereochemistry , crystal structure , crystallography , molecule , catalysis , organic chemistry , materials science , financial economics , economics , metallurgy
Acid‐catalysed hydrolysis of [CH 2 {Sn(Ph 2 )CH 2 Si(O i Pr)Me 2 } 2 ] followed by subsequent reaction with mercuric chloride in acetone afforded the novel silicon‐ and tin‐containing eight‐membered ring [ cyclo ‐CH 2 {Sn(Cl 2 )CH 2 Si(Me 2 )} 2 O] in good yield, the crystal structure of which is reported. 119 Sn NMR and X‐ray studies indicate that [ cyclo ‐CH 2 {Sn(Cl 2 )CH 2 Si(Me 2 )} 2 O] acts as a bidentate Lewis acid towards chloride ions exclusively forming the 1:1 complex [(Ph 3 P) 2 N] + [ cyclo ‐CH 2 {Sn(Cl 2 )CH 2 Si(Me 2 )} 2 OCl] − upon addition of [(Ph 3 P) 2 N] + Cl − . Also reported are the synthesis and structure of [K(dibenzo[18]crown‐6)] + [ cyclo ‐CH 2 {Sn(Cl 2 )CH 2 Si(Me 2 )} 2 OF] − , the first completely characterised organostannate with a C 2 SnCl 2 F‐ substituent pattern. No ring‐opening polymerisation could be achieved for [ cyclo ‐CH 2 {Sn(Cl 2 )CH 2 Si(Me 2 )} 2 O] or for its perphenylated derivative [ cyclo ‐CH 2 {Sn(Ph 2 )CH 2 Si(Me 2 )} 2 O]. The reaction of [ cyclo ‐CH 2 {Sn(Cl 2 )CH 2 Si(Me 2 )} 2 O] with Me 3 O + BF 4 − gave the tin‐containing fluorosilane [CH 2 {Sn(Cl 2 )CH 2 Si(F)Me 2 } 2 ], in which the Si−F bond is activated by intermolecular Si−F⋅⋅⋅Sn interactions in the solid state.