Adavanced Cleaning Products Formulations vol.4 by Flick E.W.

By Flick E.W.

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The redox reaction between RuCl3 and a cyclic 1,4-diene usually gives the ruthenium–arene dimers in high yield and purity, but this synthetic route is limited by the commercial availability or ease of synthesis of diene precursors. Thermal displacement of a coordinated arene provides another valuable synthetic route. The latter method has been employed for the synthesis of ruthenium–arenes with sterically demanding arenes such as hexamethylbenzene (hmb) and for the synthesis of amine-tethered complexes (64,68).

Consequently, the hydrolysis rates decrease with increase in the electron-accepting ability of the arene, an observation that was later confirmed for a more extensive series of compounds (75). We also studied the influence of the type of leaving group on the hydrolysis rate and found that it has a large effect. For the halides, the aquation rate was found to decrease in the order ClEBrWI. Replacement of the chloride ligand with the pseudohalide NÀ 3 even slowed down the hydrolysis rate 40-fold, while changing it for other monodentate ligands such as (substituted) pyridines or thiophenol made the hydrolysis too slow to observe.

Alternatively, arene displacement can also be photo- rather than thermally-induced. In this respect, we studied the photoactivation of the dinuclear ruthenium–arene complex [{RuCl (Z6-indane)}2(m-2,3-dpp)]2þ (2,3-dpp, 2,3-bis(2-pyridyl)pyrazine) (21). The thermal reactivity of this compound is limited to the stepwise double aquation (which shows biexponential kinetics), but irradiation of the sample results in photoinduced loss of the arene. This photoactivation pathway produces ruthenium species that are more active than their ruthenium–arene precursors (Fig.

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