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

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	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
卷号	110 期号:45 页码:12439-12442
文章类型	Article
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.
关键词	Hydrogen-terminated Silicon Self-directed Growth Alkyl Monolayers Organic Monolayers Porous Silicon Surfaces Si(111) Chemistry Functionalization Nanostructures
WOS标题词	Science & Technology ; Physical Sciences
学科领域	生物科学
关键词[WOS]	HYDROGEN-TERMINATED SILICON ; SELF-DIRECTED GROWTH ; ALKYL MONOLAYERS ; ORGANIC MONOLAYERS ; POROUS SILICON ; SURFACES ; SI(111) ; CHEMISTRY ; FUNCTIONALIZATION ; NANOSTRUCTURES
收录类别	SCI
语种	英语
WOS研究方向	Chemistry ; Physics
WOS类目	Chemistry, Physical ; Physics, Atomic, Molecular & Chemical
WOS记录号	WOS:000241893900013
引用统计	被引频次：4[WOS] [WOS记录] [WOS相关记录]
文献类型	期刊论文
条目标识符	http://210.75.249.4/handle/363003/1310
专题	中国科学院西北高原生物研究所
作者单位	1.Shandong Univ, Sch Chem & Chem Engn, Jinan 250100, Shandong, Peoples R China 2.Qufu Normal Univ, Dept Chem, Shandong 273165, Peoples R China 3.Chinese Acad Sci, NW Inst Plateau Biol, Xining 810001, Peoples R China
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,2006,110(45):12439-12442.
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,110(45),12439-12442.
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 110.45(2006):12439-12442.

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