Solvents, inert metal complexes effects

The use of supported metal complexes in transesterification reactions of TGs is not new. An earlier patent claimed that supported metals in a hydroxylated solid could effectively catalyze transesterification. The catalyst preparation used an inert hydrocarbon solvent to attach transition metal alkoxide species to the support surface. The reaction, however, was carried out in the presence of water. The author claimed that water was essential in preparing materials with good catalytic activity. Among the metals employed, titanium catalysts showed the best activity. However, it was not clear from the preparation method if reproducibility could be easily achieved, an important requirement if such catalysts were to be commercially exploited. 

According to the opinion of the authors of Ref. 32, the negative results of the experiments above do not mean that metal-free Pc could not be theoretically obtained from these precursors additional detailed studies (combination of different techniques, such as UV irradiation, microwave treatment, use of other inert solvents, electrolysis in the systems producing free radicals, etc.) are required for successful resolution of this problem. However, under the same conditions it is possible to obtain some transition metal complexes of the Pc due to the template effects (see below). 

A main question - not yet really considered - concerns the inertness of ionic liquids. Not only are the anions potential ligands, especially for neutral and cationic metal complexes one has also to take into consideration what is known for cations like (imid)azolium formation of carbene complexes via deprotonation is a rather facile process especially if ligands of sufficient basicity are present, e. g., -OR, -NR2. Therefore, several of the impressive catalytic results [113] deserve mechanistic investigation to find out whether they are really limited to the ionic liquid effects. For example, solvent and complexation effects are likely to enhance one another in the Heck coupling reactions that were run in the presence of Structure 18, Scheme 11 [115]. 

The chief advantages to using dense CO2 as the reaction medium were claimed to be its inertness, its general ability to dissolve the reactants, and its easy separation from the reaction mixture. No mechanistic work was reported, but the same mechanism as previously proposed in alkane solvents was suggested, that is, the key step was oxidative addition to the excited state of the metal complex. The C02/Rh complex system was also reported to be an effective photocatalytic system for the dehydrogenation of cyclooctane. 

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