Addition reactions of nitrones on the reconstructed C(100)-2 x 1 surfaces

NWIPB OpenIR

	Addition reactions of nitrones on the reconstructed C(100)-2 x 1 surfaces
	Wang, Zhiguo ; Wang, Honglun ; Liu, Yonjun ; Suo, Yourui
	2008-02-15
发表期刊	JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM ; Wang Zhiguo,Wang Honglun,Liu Yonjun,Suo Yourui. Addition reactions of nitrones on the reconstructed C(100)-2 x 1 surfaces.JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM,2008,850(1-3):72-78
摘要	In this paper, the reactions of nitrone, N-methyl nitrone, N-phenyl nitrone and their hydroxylamine tautomers (vinyl-hydroxylamine, N-methyl-vinyl-hydroxylamine and N-phenyl-vinyl-hydroxylamine) on the reconstructed C(100)-2 x 1 surface have been investigated using hybrid density functional theory (B3LYP), Moller-Plesset second-order perturbation (MP2) and multi-configuration complete-active-space self-consistent-field (CASSCF) methods. The calculations showed that all the nitrones can react with the surface "dimer" via facile 1.3-dipolar cycloaddition with small activation barriers (less than 12.0 kJ/mol at B3LYP/6-31g(d) level). The [2+2] cycloaddition of hydroxylamine tautomers on the C(100) surface follows a diradical mechanism. Hydroxylamine tautomers first form diradical intermediates with the reconstructed C(I 00)-2 x I surface by overcoming a large activation barrier of 50-60 kJ/mol (B3LYP), then generate [2+2] cycloaddition products via diradical transition states with negligible activation barriers. The surface reactions result in hydroxyl or amino-terminated diamond surfaces, which offers new opportunity for further modifications. (C) 2007 Elsevier B.V. All rights reserved.; In this paper, the reactions of nitrone, N-methyl nitrone, N-phenyl nitrone and their hydroxylamine tautomers (vinyl-hydroxylamine, N-methyl-vinyl-hydroxylamine and N-phenyl-vinyl-hydroxylamine) on the reconstructed C(100)-2 x 1 surface have been investigated using hybrid density functional theory (B3LYP), Moller-Plesset second-order perturbation (MP2) and multi-configuration complete-active-space self-consistent-field (CASSCF) methods. The calculations showed that all the nitrones can react with the surface "dimer" via facile 1.3-dipolar cycloaddition with small activation barriers (less than 12.0 kJ/mol at B3LYP/6-31g(d) level). The [2+2] cycloaddition of hydroxylamine tautomers on the C(100) surface follows a diradical mechanism. Hydroxylamine tautomers first form diradical intermediates with the reconstructed C(I 00)-2 x I surface by overcoming a large activation barrier of 50-60 kJ/mol (B3LYP), then generate [2+2] cycloaddition products via diradical transition states with negligible activation barriers. The surface reactions result in hydroxyl or amino-terminated diamond surfaces, which offers new opportunity for further modifications. (C) 2007 Elsevier B.V. All rights reserved.
文献类型	期刊论文
条目标识符	http://210.75.249.4/handle/363003/30353
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	Wang, Zhiguo,Wang, Honglun,Liu, Yonjun,et al. Addition reactions of nitrones on the reconstructed C(100)-2 x 1 surfaces[J]. JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM, Wang Zhiguo,Wang Honglun,Liu Yonjun,Suo Yourui. Addition reactions of nitrones on the reconstructed C(100)-2 x 1 surfaces.JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM,2008,850(1-3):72-78,2008.
APA	Wang, Zhiguo,Wang, Honglun,Liu, Yonjun,&Suo, Yourui.(2008).Addition reactions of nitrones on the reconstructed C(100)-2 x 1 surfaces.JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM.
MLA	Wang, Zhiguo,et al."Addition reactions of nitrones on the reconstructed C(100)-2 x 1 surfaces".JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM (2008).