Theoretical Study on the Mechanism for the Addition Reaction of SiH3 with Propylene and Acetic Acid
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- 作者：Yongjun Liu ; Zhiguo Wang ; Yourui Suo
- 刊名：Journal of Physical Chemistry A
- 出版年：2006
- 出版时间：November 16, 2006
- 年：2006
- 卷：110
- 期：45
- 页码：12439 - 12442
- 全文大小：131K
- 年卷期：v.110,no.45(November 16, 2006)
- ISSN：1520-5215
文摘
To explore the reactivities of alkene (-CH=CH2) and carboxy (-COOH) group with H-Si under UVirradiation, the addition mechanism for the reactions of SiH3 radical with propylene and acetic acid wasstudied by using the B3LYP/6-311++G(d,p) method. Based on the surface energy profiles, the dominantreaction pathways can be established; i.e., SiH3 adds to the terminal carbon atom of the alkene (-CH=CH2)to form an anti-Markovnikov addition product, or adds to the oxygen atom of the carboxy group (-COOH)to form silyl acetate (CH3-COOSiH3). Because the barrier in the reaction of the carboxy group (39.9 kJ/mol) is much larger than that of alkene (11.97 kJ/mol), we conclude that the reaction of bifunctional molecules(e.g., 
-alkenoic acid) with H-Si under irradiation condition is highly selective; i.e., the alkene group (-CH=CH2) reacts with SiH3 substantially faster than the carboxyl group (-COOH), which agrees well with theexperimental results. This provides the possibility of preparing carboxy-terminated monolayers on siliconsurface from -alkenoic acids via direct photochemical reaction.
-alkenoic acid) with H-Si under irradiation condition is highly selective; i.e., the alkene group (-CH=CH2) reacts with SiH3 substantially faster than the carboxyl group (-COOH), which agrees well with theexperimental results. This provides the possibility of preparing carboxy-terminated monolayers on siliconsurface from -alkenoic acids via direct photochemical reaction.