Pas de Deux of an NO Couple: Synchronous Photoswitching from a Double-Linear to a Double-Bent Ru(NO)(2) Core under Nitrosyl Charge Conservation

Hasil, Asma; Beck, Daniel; Schröder, Daniel; Pillet, Sebastien; Wenger, Emmanuel; Woike, Theo; Klüfers, Peter und Schaniel, Dominik (2022): Pas de Deux of an NO Couple: Synchronous Photoswitching from a Double-Linear to a Double-Bent Ru(NO)(2) Core under Nitrosyl Charge Conservation. In: Angewandte Chemie International Edition, Bd. 61, Nr. 42

Abstract

The {Ru(NO)(2)}(10) dinitrosylruthenium complex [Ru(NO)(2)(PPh3)(2)] (1) shows photo-induced linkage isomerism (PLI) of a special kind: the two NO ligands switch, on photo-excitation, synchronously from the ground state (GS) with two almost linear RuNO functions to a metastable state (MS) which persists up to 230 K and can be populated to approximate to 50 %. The MS was experimentally characterised by photo-crystallography, IR spectroscopy and DS-calorimetry as a double-bent variant of the double-linear GS. The experimental results are confirmed by computation which unravels the GS/MS transition as a disrotatory synchronous 50 degrees turn of the two nitrosyl ligands. Although 1 shows the usual redshift of the N-O stretch on bending the MNO unit, there is no increased charge transfer from Ru to NO along the GS-to-MS path. In terms of the effective-oxidation-state (EOS) method, both isomers of 1 and the transition state are Ru-II(NO+)(2) species.

• Dokumententyp: Zeitschriftenartikel
• Fakultät: Chemie und Pharmazie > Department Chemie
• Themengebiete: 500 Naturwissenschaften und Mathematik > 540 Chemie
• ISSN: 1433-7851
• Sprache: Englisch
• DFG: Gefördert durch die Deutsche Forschungsgemeinschaft (DFG) - 491502892