Theoretical study on the mechanism for the addition reaction of SiH3 with propylene and acetic acid

NWIPB OpenIR

	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/363003/20242
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).