DFT studies on the reaction mechanism of cis-dioxoruthenium(VI)-mediated alkene oxidation

被引：3
|
作者：
Fang, De-Cai [1 ]
机构：
[1] Beijing Normal Univ, Coll Chem, Beijing 100875, Peoples R China
来源：
STRUCTURAL CHEMISTRY | 2017年 / 28卷 / 05期
基金：
中国国家自然科学基金;
关键词：
cis-Dioxoruthenium(VI); Alkene oxidation; Reaction mechanism; DFT calculation; HYDROGEN-ATOM ABSTRACTION; RUTHENIUM-OXO COMPLEXES; H BOND ACTIVATION; POLYPYRIDYL COMPLEXES; CATALYTIC OXIDATIONS; CIS-DIHYDROXYLATION; MOLECULAR-STRUCTURE; OSMIUM TETRAOXIDE; ELECTRON-TRANSFER; BASIS-SETS;
D O I：
10.1007/s11224-017-1006-z
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
Density functional theory (DFT) calculations with the B3LYP functionals elucidated the reactivity, and mechanism of cis-dioxoruthenium(VI)-mediated alkene oxidation reaction. The most plausible reaction pathway was discussed as three distinct processes, including (1) the oxidative [3+2] cycloaddition reaction, (2) the reduction process from Ru(IV) to Ru(II), and (3) the ligand substitution to release the final product. The first process has been confirmed to be rate-determining one, since each distinct step is strongly exothermic. The electronic state of cis-dioxoruthenium(VI) and the change of the electronic state during the reaction processes are rationalized in this article.
引用
收藏
页码：1453 / 1459
页数：7
相关论文
共 50 条
  • [1] DFT studies on the reaction mechanism of cis-dioxoruthenium(VI)-mediated alkene oxidation
    De-Cai Fang
    [J]. Structural Chemistry, 2017, 28 : 1453 - 1459
  • [2] THE ELECTROCATALYTIC OXIDATION OF D(+)-GLUCOSE BY A CIS-DIOXORUTHENIUM COMPLEX
    LAI, YK
    WONG, KY
    [J]. ELECTROANALYSIS, 1994, 6 (11-12) : 919 - 924
  • [3] Kinetics and mechanisms of redox reactions of a cis-dioxoruthenium(VI) complex.
    Yau, KW
    Lau, TC
    [J]. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 1999, 218 : U739 - U739
  • [4] KINETICS OF C-H BOND AND ALKENE OXIDATION BY DIOXORUTHENIUM(VI) PORPHYRINS
    HO, C
    LEUNG, WH
    CHE, CM
    [J]. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 1992, 203 : 271 - INOR
  • [5] A NOVEL CIS-DIOXORUTHENIUM(VI) COMPLEX OF N,N',N''-TRIMETHYL-1,4,7-TRIAZACYCLONONANE (ME(3)TACN) FOR ORGANIC OXIDATION
    CHENG, WC
    YU, WY
    CHEUNG, KK
    CHE, CM
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1994, (09) : 1063 - 1064
  • [6] KINETICS AND MECHANISM OF THE OXIDATION OF IODIDE BY TRANS-DIOXORUTHENIUM(VI)
    LAU, TC
    LAU, KWC
    LAU, K
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1994, (21): : 3091 - 3093
  • [7] KINETICS OF C-H BOND AND ALKENE OXIDATION BY TRANS-DIOXORUTHENIUM(VI) PORPHYRINS
    HO, C
    LEUNG, WH
    CHE, CM
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1991, (11): : 2933 - 2939
  • [8] A KINETIC-STUDY ON THE REACTIVITY OF A CIS-DIOXORUTHENIUM(VI) COMPLEX - OXIDATION OF ALCOHOLS, AROMATIC-HYDROCARBONS, AND ALKENES BY CIS-[RU-VI(TET-ME(6))O-2](2+)
    CHENG, WC
    YU, WY
    LI, CK
    CHE, CM
    [J]. JOURNAL OF ORGANIC CHEMISTRY, 1995, 60 (21): : 6840 - 6846
  • [9] Kinetics and mechanism of the oxidation of hydroquinones by a trans-dioxoruthenium(VI) complex
    Lam, WWY
    Lee, MFW
    Lau, TC
    [J]. INORGANIC CHEMISTRY, 2006, 45 (01) : 315 - 321
  • [10] Kinetic study on the reactivity of a cis-dioxoruthenium(VI) complex. Oxidation of alcohols, aromatic hydrocarbons, and alkenes by cis-[RuVI(Tet-Me6)O2]2+
    Cheng, Wing-Chi
    Yu, Wing-Yiu
    Li, Chi-Kueng
    Che, Chi-Ming
    [J]. Journal of Organic Chemistry, 1995, 60 (21):
12345