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On the Origin of Reactivity Enhancement/Suppression upon Sequential Ligation: [Re(CO) x ] + /CH 4 ( x= 0 – 3) Couples
Author(s) -
Zhou Shaodong,
Li Jilai,
Schlangen Maria,
Schwarz Helmut
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201611826
Subject(s) - reactivity (psychology) , dehydrogenation , chemistry , rhenium , methane , hydrocarbon , ligand (biochemistry) , mass spectrometry , metal , inorganic chemistry , photochemistry , catalysis , organic chemistry , medicine , alternative medicine , pathology , biochemistry , receptor , chromatography
The thermal gas‐phase reactions of rhenium carbonyl complexes [Re(CO) x ] + ( x =0–3) with methane have been explored by using FT‐ICR mass spectrometry complemented by high‐level quantum chemical calculation. While it had been concluded in previous studies that addition of closed‐shell ligands in general decreases the reactivity of metal ions, the current work provides an exception: the previously demonstrated inertness of atomic Re + towards methane is completely changed upon ligation with CO. Both [Re(CO)] + and [Re(CO) 2 ] + bring about efficient dehydrogenation of the hydrocarbon under ambient conditions. However, addition of a third ligand to form [Re(CO) 3 ] + completely quenches the reactivity.