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.

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 ≈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° 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.