Room‐Temperature Photogeneration of Nitrosyl Linkage Isomers in Ruthenium Nitrosyl Complexes

Photoinduced linkage isomers of transition-metal nitrosyl compounds and related complexes.

The seminal discovery of light-induced changes in transition-metal nitrosyl complexes in the late 1970s and their identification as metastable linkage isomers almost 20 years after the initial discoveries have in recent years motivated a plethora of experimental and theoretical studies. They have raised the question of whether the linkage isomers play a role in the many crucial biological proce...

Photochemical nitric oxide precursors: synthesis, photochemistry, and ligand substitution kinetics of ruthenium salen nitrosyl and ruthenium salophen nitrosyl complexes.

Described are syntheses, characterizations, and photochemical reactions of the nitrosyl complexes Ru(salen)(ONO)(NO) (I, salen = N,N'-ethylenebis(salicylideneiminato) dianion), Ru(salen)(Cl)(NO) (II), Ru((t)Bu(4)salen)(Cl)(NO) (III,(t)Bu(4)salen = N,N'-ethylenebis(3,5-di-tert-butylsalicylideneiminato) dianion), Ru((t)Bu(4)salen)(ONO)(NO) (IV), Ru((t)Bu(2)salophen)(Cl)(NO) (V, (t)Bu(2)salophen =...

Photocrystallography reveals new metastable nitrosyl linkage isomers in the solid state

Using the combined techniques of photocrystallography and infrared spectroscopy is a very powerful method for generating and establishing the structures of metastable linkage isomers in the solid state as exemplified by the work of Casaretto et al. [IUCrJ (2015), 2, 35-44] on [RuCl(NO)2(PPh3)2]BF4.

The Electron Transfer Chemistry of Nitrosyl Complexes

The reactions of nitrosyl complexes with cysteine.

The reaction kinetics of a set of ruthenium nitrosyl complexes, {(X)5MNO}n, containing different coligands X (polypyridines, NH3, EDTA, pz, and py) with cysteine (excess conditions), were studied by UV-vis spectrophotometry, using stopped-flow techniques, at an appropriate pH, in the range 3-10, and T = 25 degrees C. The selection of coligands afforded a redox-potential range from -0.3 to +0.5 ...