Synthesis and Characterization of Ferrocenyl-Modified Mesoporous Silicates
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- 作者：Stephen O'Brien ; Julian M. Keates ; Stephen Barlow ; Mark J. Drewitt ; Benjamin R. Payne ; and Dermot O'Hare
- 刊名：Chemistry of Materials
- 出版年：1998
- 出版时间：December 1998
- 年：1998
- 卷：10
- 期：12
- 页码：4088 - 4099
- 全文大小：238K
- 年卷期：v.10,no.12(December 1998)
- ISSN：1520-5002
文摘
The mesoporous silicates MCM-41 and FSM-16 have been functionalized with a range offerrocenyl groups. The general synthetic methodology involves either reaction of the strained[1]ferrocenophanes [Fe(
-C5R4)2SiMe2] (R = H or Me), [Fe(-C9Me6)(-C5H4)SiMe2], or theferrocenyl carbocation [Fe(-C5Me5)(-C5Me4CH2)]+ with the dehydrated mesoporous silicate.The materials have been extensively characterized by (inter alia) solid-state 13C and 29SiNMR and Fe K-edge EXAFS spectroscopy. The reaction of either [Fe(-C5H4)2SiMe2] or [Fe(-C5Me4)2SiMe2] with MCM-41 affords both single ferrocenyl and short chain oligo(ferrocenyl)units grafted to the silicate walls of the mesopores. In contrast, the reaction of [Fe(-C9Me5)(-C5H4)SiMe2] with MCM-41 gives only a single type of ferrocenyl group attached tothe pore walls via a regiospecific ring-opening reaction in which the Si-(C5H4) bond is brokenin preference to the Si-(C9Me6) bond.
-C5R4)2SiMe2] (R = H or Me), [Fe(-C9Me6)(-C5H4)SiMe2], or theferrocenyl carbocation [Fe(-C5Me5)(-C5Me4CH2)]+ with the dehydrated mesoporous silicate.The materials have been extensively characterized by (inter alia) solid-state 13C and 29SiNMR and Fe K-edge EXAFS spectroscopy. The reaction of either [Fe(-C5H4)2SiMe2] or [Fe(-C5Me4)2SiMe2] with MCM-41 affords both single ferrocenyl and short chain oligo(ferrocenyl)units grafted to the silicate walls of the mesopores. In contrast, the reaction of [Fe(-C9Me5)(-C5H4)SiMe2] with MCM-41 gives only a single type of ferrocenyl group attached tothe pore walls via a regiospecific ring-opening reaction in which the Si-(C5H4) bond is brokenin preference to the Si-(C9Me6) bond.