Novel Silicon- and Tin-Containing Ferrocenophanes and Related Compounds as Lewis Acids
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- 作者：Reiner Altmann ; Olivier Gausset ; Dagmar Horn ; Klaus Jurkschat ; Markus Schü ; rmann ; Marco Fontani ; and Piero Zanello
- 刊名：Organometallics
- 出版年：2000
- 出版时间：February 21, 2000
- 年：2000
- 卷：19
- 期：4
- 页码：430 - 443
- 全文大小：461K
- 年卷期：v.19,no.4(February 21, 2000)
- ISSN：1520-6041
文摘
The syntheses of 1,1'-bis(chloromethyldimethylsilyl)ferrocene, fc(SiMe2CH2Cl)2 (2), of theseries of open-chain ferrocene- and silicon-containing organotin(IV) compounds (FcMe2SiCH2)2SnPh2 (3), (FcMe2SiCH2SnXPh)2CH2 (4, X = Ph; 7, X = I; 8, X = Cl; 9, X = F), fc(SiMe2CH2SnXR2)2 (5, R = X = Ph; 6, R = X = Me; 10, R = Ph, X = I; 11, R = Me, X = Cl;12, R = Ph, X = Cl; 13, R = Ph, X = F), fc(SiMe2CH2SnPh2CH2SiMe2Fc)2 (14), and of theferrocenophanes [fc(SiMe2CH2SnXRCH2SiMe2)2fc] (15, R = X = Me; 16, R = X = Ph; 17, R= Ph, X = I; 18, R = Ph, X = F; 19, R = Ph, X = Cl; 20, R = Me, X = Cl) and two of theirchloride complexes {[fc(SiMe2CH2SnClRCH2SiMe2)2fc·2Cl]2- 2[(Ph3P)2N]+} (22, R = Me; 23,R = Ph) are reported, and the molecular structures of 4, 16, 17, 19, 20, 22, and 23 aredescribed. In solution, the halogen-substituted ferrocenophanes 17-19 undergo cis-transisomerization, the rate of which is enhanced by addition of halide ions. Variable-temperature119Sn and 19F NMR studies in solution indicate that the fluoro derivatives 9, 13, and 18react with different molar equivalents of fluoride ions to give the 1:1 and 1:2 adducts[(FcMe2SiCH2SnFPh)2CH2·nF]n-[Bu4N]+n (9a,b, n = 1; 9c, n = 2), {[13·2F]2-[Bu4N]+2}, and{[18·F]-[Bu4N]+} and {[18·2F]2-[Bu4N]+2}, respectively. A more extended electrochemicalinvestigation points out that the species containing halogen-substituted tin groups are moresensitive to anions than their analogues containing diphenyltin groups.