Premium
Thermal Ethane Activation by Bare [V 2 O 5 ] + and [Nb 2 O 5 ] + Cluster Cations: on the Origin of Their Different Reactivities
Author(s) -
Wu XiaoNan,
Tang ShiYa,
Zhao HaiTao,
Weiske Thomas,
Schlangen Maria,
Schwarz Helmut
Publication year - 2014
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201402055
Subject(s) - chemistry , bond dissociation energy , reactivity (psychology) , dissociation (chemistry) , density functional theory , vanadium , hydrogen , metal , thermal decomposition , hydrocarbon , crystallography , inorganic chemistry , computational chemistry , medicine , alternative medicine , organic chemistry , pathology
The gas‐phase reactivity of [V 2 O 5 ] + and [Nb 2 O 5 ] + towards ethane has been investigated by means of mass spectrometry and density functional theory (DFT) calculations. The two metal oxides give rise to the formation of quite different reaction products; for example, the direct room‐temperature conversions C 2 H 6 →C 2 H 5 OH or C 2 H 6 →CH 3 CHO are brought about solely by [V 2 O 5 ] + . In distinct contrast, for the couple [Nb 2 O 5 ] + /C 2 H 6 , one observes only single and double hydrogen‐atom abstraction from the hydrocarbon. DFT calculations reveal that different modes of attack in the initial phase of CH bond activation together with quite different bond‐dissociation energies of the MO bonds cause the rather varying reactivities of [V 2 O 5 ] + and [Nb 2 O 5 ] + towards ethane. The gas‐phase generation of acetaldehyde from ethane by bare [V 2 O 5 ] + may provide mechanistic insight in the related vanadium‐catalyzed large‐scale process.