Gas-Phase Reactions of Cationic Vanadium-Phosphorus Oxide Clusters with C2Hx (x=4, 6): A DFT-Based Analysis of Reactivity Patterns

被引：23

作者：

Dietl, Nicolas ^{[1
]}

Zhang, Xinhao ^{[1
,3
]}

van der Linde, Christian ^{[2
]}

Beyer, Martin K. ^{[2
]}

Schlangen, Maria ^{[1
]}

Schwarz, Helmut ^{[1
,4
]}

机构：

[1] Tech Univ Berlin, Inst Chem, D-10623 Berlin, Germany

[2] Univ Kiel, Inst Phys Chem, D-24098 Kiel, Germany

[3] Peking Univ, Shenzhen Grad Sch, Lab Chem Genom, Lab Computat Chem & Drug Design, Shenzhen 518055, Peoples R China

[4] King Abdulaziz Univ, Fac Sci, Dept Chem, Jeddah 21589, Saudi Arabia

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2013年 / 19卷 / 09期

基金：

美国国家科学基金会;

关键词：

CH activation; cluster compounds; density functional calculations; gas-phase reactions; reaction mechanisms; N-BUTANE OXIDATION; HYDROGEN-ATOM ABSTRACTION; H BOND ACTIVATION; MECHANISTIC ASPECTS; METHANE ACTIVATION; MALEIC-ANHYDRIDE; VIBRATIONAL SPECTROSCOPY; HYDROCARBON CONVERSION; SELECTIVE OXIDATION; THERMAL-ACTIVATION;

D O I：

10.1002/chem.201203050

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The reactivities of the adamantane-like heteronuclear vanadium-phosphorus oxygen cluster ions [VxP4xO10].+ (x=0, 24) towards hydrocarbons strongly depend on the V/P ratio of the clusters. Possible mechanisms for the gas-phase reactions of these heteronuclear cations with ethene and ethane have been elucidated by means of DFT-based calculations; homolytic CH bond activation constitutes the initial step, and for all systems the PO. unit of the clusters serves as the reactive site. More complex oxidation processes, such as oxygen-atom transfer to, or oxidative dehydrogenation of the hydrocarbons require the presence of a vanadium atom to provide the electronic prerequisites which are necessary to bring about the 2e reduction of the cationic clusters.

引用

页码：3017 / 3028

页数：12