Hydrocarbon ligand-free system

In real systems (hydrocarbon-02-catalyst), various oxidation products, such as alcohols, aldehydes, ketones, bifunctional compounds, are formed in the course of oxidation. Many of them readily react with ion-oxidants in oxidative reactions. Therefore, radicals are generated via several routes in the developed oxidative process, and the ratio of rates of these processes changes with the development of the process [5], The products of hydrocarbon oxidation interact with the catalyst and change the ligand sphere around the transition metal ion. This phenomenon was studied for the decomposition of sec-decyl hydroperoxide to free radicals catalyzed by cupric stearate in the presence of alcohol, ketone, and carbon acid [70-74], The addition of all these compounds was found to lower the effective rate constant of catalytic hydroperoxide decomposition. The experimental data are in agreement with the following scheme of the parallel equilibrium reactions with the formation of Cu-hydroperoxide complexes with a lower activity. 

Similarly, benzylidene(pentacarbonyl) complexes of chromium and tungsten react with cyclo-pentadiene, by stereoselective transfer of the benzylidene moiety to one of the C-C double bonds of the diene, to form coordinated e do-6-phenylbicyclo[3.1.0]hex-2-ene 9 with the metal-ligand unit complexing from the exo side. This method was applied to several other dienes. Reaction with cyclohexa-1,3-diene gave the corresponding cndo-7-phenylbicyclo[4.1.0]hept-2-ene complex. The cyclopropane-containing ligands obtained in this way were liberated from the complex to form the free hydrocarbon system. 

---