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Tuning the Reactivities of the Heteronuclear [Al n V 3− n O 7− n ] + ( n= 1, 2) Cluster Oxides towards Methane by Varying the Composition of the Metal Centers
Author(s) -
Zhou Shaodong,
Sun Xiaoyan,
Yue Lei,
Schlangen Maria,
Schwarz Helmut
Publication year - 2019
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.201805908
Subject(s) - heteronuclear molecule , fourier transform ion cyclotron resonance , methane , chemistry , oxidizing agent , formaldehyde , mass spectrometry , ion , analytical chemistry (journal) , stoichiometry , inorganic chemistry , nuclear magnetic resonance spectroscopy , stereochemistry , organic chemistry , chromatography
Abstract The thermal gas‐phase reactions of [Al 2 VO 5 ] + and [AlV 2 O 6 ] + with methane have been explored by using Fourier transform ion cyclotron resonance (FT‐ICR) mass spectrometry complemented by high‐level quantum chemical calculations. Both cluster ions chemisorbed methane as the major reaction channels at room temperature. [Al 2 VO 5 ] + could break only one C−H bond to liberate CH 3 , whereas [AlV 2 O 6 ] + exhibited higher oxidizing ability such that it brings about the selective generation of formaldehyde. Mechanistic aspects are revealed and the crucial roles of the metal centers are discussed.