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On the Origin of Reactivity Enhancement/Suppression upon Sequential Ligation: [Re(CO)x ]+ /CH4 (x=0-3) Couples
Shaodong Zhou1, Jilai Li1,2, Maria Schlangen1
1Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 135, 10623, Berlin, Germany.
Abstract:
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.
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