title: On the Origin of Reactivity Enhancement/Suppression upon Sequential Ligation: [Re(CO)x]+/CH4(x=0-3) Couples.
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.
authors.affiliation: Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 135, 10623, Berlin, Germany.
authors.forename: Shaodong
authors.initials: S
authors.lastname: Zhou
authors.affiliation: Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 135, 10623, Berlin, Germany.|Institute of Theoretical Chemistry, Jilin University, Changchun, 130023, P.R. China.
authors.forename: Jilai
authors.initials: J
authors.lastname: Li
authors.affiliation: Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 135, 10623, Berlin, Germany.
authors.forename: Maria
authors.initials: M
authors.lastname: Schlangen
authors.affiliation: Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 135, 10623, Berlin, Germany.
authors.forename: Helmut
authors.identifier: 0000-0002-3369-7997
authors.initials: H
authors.lastname: Schwarz
keywords: gas-phase reactions; ligand effects; methane activation; quantum chemical calculation