Theoretical Study of the Oxidation of Methane to Methanol by the [(CuCuII)-Cu-II(mu-O)(2)Cu-III(7-N-Etppaz)](1+) Complex

doi:10.1021/acs.inorgchem.8b00054

QIBEBT-IR

	Theoretical Study of the Oxidation of Methane to Methanol by the [(CuCuII)-Cu-II(mu-O)(2)Cu-III(7-N-Etppaz)](1+) Complex
	Liu, Yan Fang 1; Du, Likai2
	2018-03-19
发表期刊	INORGANIC CHEMISTRY
ISSN	0020-1669
卷号	57 期号:6 页码:3261-3271
摘要	The reactivity patterns of a series of trivalent copper complexes have been studied to gain a better understanding of the chemical reactions occurring at the active site of particulate methane monooxygenase (pMMO). In this study, hybrid density functional theory is used to study the oxidation of methane to methanol mediated by the [(CuCuII)-Cu-II(mu-O)(2)Cu-III(7-N-Etppz)](1+) complex. Reaction mechanisms in different spin states were explored. Based on the calculated free-energy profile, a mechanism is suggested for the reaction of the oxidation of methane to methanol. The first step (1 -> 2) is a hydrogen transfer to the bridged oxygen in the Cu2O2 core from the methane to form a methyl radical. The second step (2 -> 3) is the radical recombination, in which the bridged hydroxyl rotates upward and exposes the oxygen moiety toward the methyl radical to form methanol. The radical recombination step is rate-limiting, with a calculated free-energy barrier of 19.6 kcal mol(-1), which is in good agreement with the experimental value of 18.4 kcal mol(-1). The mixed valent bis(mu-oxo)(CuCuIII)-Cu-II species in the Cu3O4 core is directly responsible for the C-H activation of methane.
文章类型	Article
WOS标题词	Science & Technology ; Physical Sciences
DOI	10.1021/acs.inorgchem.8b00054
关键词[WOS]	DICOPPER SITE ; MONOOXYGENASE ; HYDROXYLATION ; DENSITY ; CONVERSION ; REACTIVITY ; SPECTROSCOPY ; ACTIVATION ; MECHANISM ; DFT
收录类别	SCI
语种	英语
WOS研究方向	Chemistry
项目资助者	National Science Foundation of China(21607164 ; 21503249)
WOS类目	Chemistry, Inorganic & Nuclear
WOS记录号	WOS:000428219500038
出版者	AMER CHEMICAL SOC
引用统计
文献类型	期刊论文
条目标识符	http://ir.qibebt.ac.cn/handle/337004/10802
专题	中国科学院青岛生物能源与过程研究所
通讯作者	Liu, Yan Fang; Du, Likai
作者单位	1.Chinese Acad Sci, Qingdao Inst Bioenergy & Bioproc Technol, Qingdao Key Lab Solar Energy Utilizat & Energy St, Key Lab Biobased Mat, Qingdao 266101, Shandong, Peoples R China 2.Huazhong Agr Univ, Coll Informat, Hubei Key Lab Agr Bioinformat, Wuhan 430070, Hubei, Peoples R China
推荐引用方式 GB/T 7714	Liu, Yan Fang,Du, Likai. Theoretical Study of the Oxidation of Methane to Methanol by the [(CuCuII)-Cu-II(mu-O)(2)Cu-III(7-N-Etppaz)](1+) Complex[J]. INORGANIC CHEMISTRY,2018,57(6):3261-3271.
APA	Liu, Yan Fang,&Du, Likai.(2018).Theoretical Study of the Oxidation of Methane to Methanol by the [(CuCuII)-Cu-II(mu-O)(2)Cu-III(7-N-Etppaz)](1+) Complex.INORGANIC CHEMISTRY,57(6),3261-3271.
MLA	Liu, Yan Fang,et al."Theoretical Study of the Oxidation of Methane to Methanol by the [(CuCuII)-Cu-II(mu-O)(2)Cu-III(7-N-Etppaz)](1+) Complex".INORGANIC CHEMISTRY 57.6(2018):3261-3271.