Room-Temperature C-H Bond Activation of Methane by Bare [P4O10]•+

被引:106
作者
Dietl, Nicolas [1 ]
Engeser, Marianne [2 ]
Schwarz, Helmut [1 ]
机构
[1] Tech Univ Berlin, Inst Chem, D-10623 Berlin, Germany
[2] Univ Bonn, Kekule Inst Organ Chem & Biochem, D-5300 Bonn, Germany
关键词
C-H activation; cluster compounds; density functional calculations; gas-phase reactions; radicals; CATALYTIC-OXIDATION REACTIONS; METAL-OXIDE CLUSTERS; GAS-PHASE; REACTIVITY; CATIONS; OXYGEN; ETHYLENE; STATE; CH4; MOLYBDENUM;
D O I
10.1002/anie.200901596
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
No need for a metal: A combination of mass spectrometry and computational studies (density functional theory and coupled-cluster methods) shows that [P4O10].+ is the first polynuclear nonmetal oxide cation that is capable of activating the C-H bond of methane at room temperature (see picture). This process represents a further example in the reactivity of oxygencentered radicals. © 2009 Wiley-VCH Verlag GmbH & Co. KGaA.
引用
收藏
页码:4861 / 4863
页数:3
相关论文
共 55 条
[1]  
BAKELLS D, 2008, INORG CHEM, V47, P10090
[2]  
BAKELLS D, 2009, CHEM COMMUN, P1772
[3]  
BAKELLS D, 2008, CHEM COMMUN, P744
[4]   OXIDATIVE COUPLING OF METHANE ON SILVER CATALYSTS [J].
BAO, X ;
MUHLER, M ;
SCHLOGL, R ;
ERTL, G .
CATALYSIS LETTERS, 1995, 32 (1-2) :185-194
[5]   EMPIRICAL-METHODS FOR DETERMINATION OF IONIZATION GAUGE RELATIVE SENSITIVITIES FOR DIFFERENT GASES [J].
BARTMESS, JE ;
GEORGIADIS, RM .
VACUUM, 1983, 33 (03) :149-153
[6]   3 METHODS TO MEASURE RH BOND-ENERGIES [J].
BERKOWITZ, J ;
ELLISON, GB ;
GUTMAN, D .
JOURNAL OF PHYSICAL CHEMISTRY, 1994, 98 (11) :2744-2765
[7]   Gas-phase reactions of rhenium-oxo species ReOn+, n=0, 2-6, 8, with O2, N2O, CO, H2O, H2, CH4 and C2H4 [J].
Beyer, MK ;
Berg, CB ;
Bondybey, VE .
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2001, 3 (10) :1840-1847
[8]   NEW MECHANISMS FOR CHEMISTRY AT SURFACES [J].
CEYER, ST .
SCIENCE, 1990, 249 (4965) :133-139
[9]   Chemically induced fast solid-state transitions of ω-VOPO4 in vanadium phosphate catalysts [J].
Conte, Marco ;
Budroni, Gerolamo ;
Bartley, Jonathan K. ;
Taylor, Stuart H. ;
Carley, Albert F. ;
Schmidt, Andi ;
Murphy, Damien M. ;
Girgsdies, Frank ;
Ressler, Thorsten ;
Schloegl, Robert ;
Hutchings, Graham J. .
SCIENCE, 2006, 313 (5791) :1270-1273
[10]   Methane Activation by Metal-Free Radical Cations: Experimental Insight into the Reaction Intermediate [J].
de Petris, Giulia ;
Troiani, Anna ;
Rosi, Marzio ;
Angelini, Giancarlo ;
Ursini, Ornella .
CHEMISTRY-A EUROPEAN JOURNAL, 2009, 15 (17) :4248-4252