C-H bond activation by nanosized scandium oxide clusters in gas-phase

doi:10.1016/j.ijms.2011.11.011

CORC > 化学研究所 > 中国科学院化学研究所

	C-H bond activation by nanosized scandium oxide clusters in gas-phase
	Wu, Xiao-Nan 1,2; Xu, Bo 1,2; Meng, Jing-Heng 1,2; He, Sheng-Gui 1
刊名	INTERNATIONAL JOURNAL OF MASS SPECTROMETRY
	2012-01-15
卷号	310 页码:57-64
关键词	C-h Bond Activation Mass Spectrometry Density Functional Calculation Oxygen-centred Radical Atomic Cluster Scandium Oxide
ISSN号	1387-3806
DOI	10.1016/j.ijms.2011.11.011
英文摘要	Scandium oxide cluster cations are prepared by laser ablation and reacted with n-butane in a fast flow reactor. A reflectron time-of-flight mass spectrometer is built to detect the cluster distribution before and after the reactions. Hydrogen atom abstraction (HAA) products (Sc2O3)(N)H+ (N = 1-22), (Sc2O3)(N)O4H+ (N = 4-22) and their deuterated compounds are observed upon the cluster interactions with n-C4H10 and n-C4D10, respectively. This indicates that C-H bond activation of n-butane over atomic clusters as large as Sc44O66+ and Sc44O70+ can take place in gas phase. The experimentally determined rate constants and values of kinetic isotopic effect for HAA vary significantly with the cluster sizes. Density functional theory (DFT) calculations are performed to study the structures and reactivity of small clusters (Sc2O3)(1-3)(+). The DFT results suggest that the experimentally observed C-H bond activation by (Sc2O3)(N)(+) is facilitated by oxygen-centred radicals bridgingly bonded in the clusters. The nature of unpaired spin density distributions within the clusters may be responsible for the experimentally observed size-dependent reactivity. (C) 2011 Elsevier B.V. All rights reserved.
语种	英语
出版者	ELSEVIER SCIENCE BV
WOS记录号	WOS:000300597400007
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/48359]
专题	中国科学院化学研究所
通讯作者	He, Sheng-Gui
作者单位	1.Chinese Acad Sci, Beijing Natl Lab Mol Sci, State Key Lab Struct Chem Unstable & Stable Speci, Inst Chem, Beijing 100190, Peoples R China 2.Chinese Acad Sci, Grad Sch, Beijing 100039, Peoples R China
推荐引用方式 GB/T 7714	Wu, Xiao-Nan,Xu, Bo,Meng, Jing-Heng,et al. C-H bond activation by nanosized scandium oxide clusters in gas-phase[J]. INTERNATIONAL JOURNAL OF MASS SPECTROMETRY,2012,310:57-64.
APA	Wu, Xiao-Nan,Xu, Bo,Meng, Jing-Heng,&He, Sheng-Gui.(2012).C-H bond activation by nanosized scandium oxide clusters in gas-phase.INTERNATIONAL JOURNAL OF MASS SPECTROMETRY,310,57-64.
MLA	Wu, Xiao-Nan,et al."C-H bond activation by nanosized scandium oxide clusters in gas-phase".INTERNATIONAL JOURNAL OF MASS SPECTROMETRY 310(2012):57-64.