Knowledge Management System of Northwest Institute of Plateau Biology, CAS
Theoretical study on the mechanism for the addition reaction of SiH3 with propylene and acetic acid | |
Liu, Yongjun ; Wang, Zhiguo ; Suo, Yourui | |
2006-11-16 | |
发表期刊 | JOURNAL OF PHYSICAL CHEMISTRY A ; Liu Yongjun, Wang Zhiguo, Suo Yourui.Theoretical study on the mechanism for the addition reaction of SiH3 with propylene and acetic acid.JOURNAL OF PHYSICAL CHEMISTRY A,2006,110(45):12439-12442 |
摘要 | To explore the reactivities of alkene (-CH=CH2) and carboxy (-COOH) group with H-Si under UV irradiation, the addition mechanism for the reactions of SiH3 radical with propylene and acetic acid was studied by using the B3LYP/6-311++ G(d,p) method. Based on the surface energy profiles, the dominant reaction 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., omega-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 the experimental results. This provides the possibility of preparing carboxy-terminated monolayers on silicon surface from omega-alkenoic acids via direct photochemical reaction.; To explore the reactivities of alkene (-CH=CH2) and carboxy (-COOH) group with H-Si under UV irradiation, the addition mechanism for the reactions of SiH3 radical with propylene and acetic acid was studied by using the B3LYP/6-311++ G(d,p) method. Based on the surface energy profiles, the dominant reaction 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., omega-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 the experimental results. This provides the possibility of preparing carboxy-terminated monolayers on silicon surface from omega-alkenoic acids via direct photochemical reaction. |
文献类型 | 期刊论文 |
条目标识符 | http://210.75.249.4/handle/363003/45706 |
专题 | 中国科学院西北高原生物研究所 |
推荐引用方式 GB/T 7714 | Liu, Yongjun,Wang, Zhiguo,Suo, Yourui. Theoretical study on the mechanism for the addition reaction of SiH3 with propylene and acetic acid[J]. JOURNAL OF PHYSICAL CHEMISTRY A, Liu Yongjun, Wang Zhiguo, Suo Yourui.Theoretical study on the mechanism for the addition reaction of SiH3 with propylene and acetic acid.JOURNAL OF PHYSICAL CHEMISTRY A,2006,110(45):12439-12442,2006. |
APA | Liu, Yongjun,Wang, Zhiguo,&Suo, Yourui.(2006).Theoretical study on the mechanism for the addition reaction of SiH3 with propylene and acetic acid.JOURNAL OF PHYSICAL CHEMISTRY A. |
MLA | Liu, Yongjun,et al."Theoretical study on the mechanism for the addition reaction of SiH3 with propylene and acetic acid".JOURNAL OF PHYSICAL CHEMISTRY A (2006). |
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