Transition metal ions with hydrocarbons

Exothermic Reactions of Transition Metal Ions with Hydrocarbons. Cross sections for the formation of product ions resulting from the interaction of Ni+ with n-butane are shown in Figure 6 for a range of relative kinetic energies between 0.2 and 4 eV. In contrast to the results shown in Figure 3, several products (reactions 6-8) are formed with large cross section at low energies. These cross sections decrease with... 

Variable valence transition metal ions, such as Co VCo and Mn /Mn are able to catalyze hydrocarbon autoxidations by increasing the rate of chain initiation. Thus, redox reactions of the metal ions with alkyl hydroperoxides produce chain initiating alkoxy and alkylperoxy radicals (Fig. 6). Interestingly, aromatic percarboxylic acids, which are key intermediates in the oxidation of methylaromatics, were shown by Jones (ref. 10) to oxidize Mn and Co, to the corresponding p-oxodimer of Mn or Co , via a heterolytic mechanism (Fig. 6). 

Retard efficiently oxidation of polymers catalysed by metal impurities. Function by chelation. Effective metal deactivators are complexing agents which have the ability to co-ordinate the vacant orbitals of transition metal ions to their maximum co-ordination number and thus inhibit co-ordination of hydroperoxides to metal ions. Main use of stabilisation against metal-catalysed oxidation is in wire and cable applications where hydrocarbon materials are in contact with metallic compounds, e.g. copper. 

Considerable interest in the subject of C-H bond activation at transition-metal centers has developed in the past several years (2), stimulated by the observation that even saturated hydrocarbons can react with little or no activation energy under appropriate conditions. Interestingly, gas phase studies of the reactions of saturated hydrocarbons at transition-metal centers were reported as early as 1973 (3). More recently, ion cyclotron resonance and ion beam experiments have provided many examples of the activation of both C-H and C-C bonds of alkanes by transition-metal ions in the gas phase (4). These gas phase studies have provided a plethora of highly speculative reaction mechanisms. Conventional mechanistic probes, such as isotopic labeling, have served mainly to indicate the complexity of "simple" processes such as the dehydrogenation of alkanes (5). More sophisticated techniques, such as multiphoton infrared laser activation (6) and the determination of kinetic energy release distributions (7), have revealed important features of the potential energy surfaces associated with the reactions of small molecules at transition metal centers. 

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. 

Many carbon compounds have been reacted with bare transition metal ions (9) but in most studies C-C or C-H scission was the desired process under investigation. Simple addition complex ions with hydrocarbons have been observed but only a few complexes with benzene and C60 will be mentioned here. 

The four remaining papers all deal with the catalysis of liquid-phase oxidation processes by transition metal ions (6). A. T. Betts and N. Uri show in particular how metal complexes can either catalyze or inhibit oxidation according to their concentration. In this investigation, various hydrocarbons (especially 2,6,10,14-tetramethylpentadecane) were used as substrates, and metal ions were present either as salicylaldimine or di-isopropylsalicylate chelates. These compounds are considerably soluble in non-polar media, and this makes it possible to examine their effect over a much wider range of concentration than is usually accessible in this type of work. These studies show that catalyst-inhibitor conversion is always... 

The H-abstraction reaction, however, does not determine selectivity entirely. Depending on the experimental conditions, as discussed earlier, butadiene desorption could be one important step. In this case, the electronic properties of the transition metal ions that determine the interaction with the unsaturated hydrocarbon have to be considered. 

The cleavage of the C—H bond by direct participation of a transition metal ion proceeds via an oxidative addition mechanism or an electrophilic substitution mechanism. Metals in low oxidation states undergo oxidative addition while high oxidation state metals take part in electrophilic substitutions. Another function of the metal complex in these reactions consists of abstracting an electron or a hydrogen atom from the hydrocarbon, RH. The RH radical ions or R radicals which are formed then interact with other species, such as molecular oxygen which is present in the solution or in one of the ligands of the metal complex (21). 

The number of monodentate groups such as hydroxide, halide, water molecule, etc., bonded to a central metal ion, usually equates to its coordination number. However, a remarkable feature occurs if two or more of these ligand donor groups are united, possibly by a short chain of hydrocarbons there will be a markedly enhanced preference for forming such bidentate complexes with the transition metal ion, and indeed in the ultimate, it is possible to go through tri- to tetra- to penta-to hexadentate chelate ligands such as EDTA (ethylenediaminetetra-acetic acid) which is widely described in this book. 

Characteristic features of vanadium containing heteropoly catalysts for the selective oxidation of hydrocarbons have been described. MAA yield ftom isobutyric acid was successfully enhanced by the stabilization of the vanadium-substituted heteropolyanions by forming cesium salts. As for lower alkane oxidation by using vanadium containing heteropoly catalysts, it was found that the surface of (V0)2P207 was reversibly oxidized to the Xi (8) phase under the reaction conditions of n-butane oxidation. The catalytic properties of cesium salts of 12-heteropolyacids were controlled by the substitution with vanadium, the Cs salt formation, and the addition of transition metal ions. By this way, the yield of MAA from isobutane reached 9.0%. Furthermore, vanadium-substituted 12-molybdates in solution showed 93% conversion on H2O2 basis in hydroxylation of benzene to phenol with 100% selectivity on benzene basis. 

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