Catalysts metal complex oxidation

J. Guzman and B. C. Gates, Supported molecular catalysts metal complexes and clusters on oxides and zeolites, Dalton Trans. 17, 3303—3318 (2003). 

Influence of Solubility and Structure on the Activity of Metal Complex Oxidation Catalysts... 

Sherrington, D. C. Polymer-supported metal complex oxidation catalysts. Pure Appl. Chem. 1988, 60, 401-414. 

Polystyrene-based resins have been used widely as supports for metal complex catalysts and other reactive species. These polymers, however, have a drawback in their limited thermo-oxidative stability [1,2]. The scope for application is therefore restricted, particularly in polymer-supported transition metal complex oxidation catalysts [3]. Consequently there is a need for the development of polymer supports with a much higher intrinsic thermo-oxidative stability. Polybenzimidazoles and polyimides are likely candidates in this respect. 

The perovskite-type catalysts (ref.l), other non noble metal complex oxides catalysts (ref.2), and mixed metal oxides catalysts (ref.3) have been studied in our laboratory. The various preparation techniques of catalysts (ref.4 and 5), the adsorption and thermal desorption of CO, C2H5 and O2 (ref.6 and 7), the reactivity of lattice oxygen (ref.8), the electric conductance of catalysts (ref.9), the pattern of poisoning by SO2 (ref. 10 and 11), the improvement of crushing strength of support (ref. 12) and determination of the activated surface of complex metal oxides (ref. 13) have also been reported. 

Pd-cataly2ed reactions of butadiene are different from those catalyzed by other transition metal complexes. Unlike Ni(0) catalysts, neither the well known cyclodimerization nor cyclotrimerization to form COD or CDT[1,2] takes place with Pd(0) catalysts. Pd(0) complexes catalyze two important reactions of conjugated dienes[3,4]. The first type is linear dimerization. The most characteristic and useful reaction of butadiene catalyzed by Pd(0) is dimerization with incorporation of nucleophiles. The bis-rr-allylpalladium complex 3 is believed to be an intermediate of 1,3,7-octatriene (7j and telomers 5 and 6[5,6]. The complex 3 is the resonance form of 2,5-divinylpalladacyclopentane (1) and pallada-3,7-cyclononadiene (2) formed by the oxidative cyclization of butadiene. The second reaction characteristic of Pd is the co-cyclization of butadiene with C = 0 bonds of aldehydes[7-9] and CO jlO] and C = N bonds of Schiff bases[ll] and isocyanate[12] to form the six-membered heterocyclic compounds 9 with two vinyl groups. The cyclization is explained by the insertion of these unsaturated bonds into the complex 1 to generate 8 and its reductive elimination to give 9. 

Today the most efficient catalysts are complex mixed metal oxides that consist of Bi, Mo, Fe, Ni, and/or Co, K, and either P, B, W, or Sb. Many additional combinations of metals have been patented, along with specific catalyst preparation methods. Most catalysts used commercially today are extmded neat metal oxides as opposed to supported impregnated metal oxides. Propylene conversions are generally better than 93%. Acrolein selectivities of 80 to 90% are typical. 

Early catalysts for acrolein synthesis were based on cuprous oxide and other heavy metal oxides deposited on inert siHca or alumina supports (39). Later, catalysts more selective for the oxidation of propylene to acrolein and acrolein to acryHc acid were prepared from bismuth, cobalt, kon, nickel, tin salts, and molybdic, molybdic phosphoric, and molybdic siHcic acids. Preferred second-stage catalysts generally are complex oxides containing molybdenum and vanadium. Other components, such as tungsten, copper, tellurium, and arsenic oxides, have been incorporated to increase low temperature activity and productivity (39,45,46). 

Reactions 33 and 35 constitute the two principal reactions of alkyl hydroperoxides with metal complexes and are the most common pathway for catalysis of LPOs (2). Both manganese and cobalt are especially effective in these reactions. There is extensive evidence that the oxidation of intermediate ketones is enhanced by a manganese catalyst, probably through an enol mechanism (34,96,183—185). 

The first-stage catalysts for the oxidation to methacrolein are based on complex mixed metal oxides of molybdenum, bismuth, and iron, often with the addition of cobalt, nickel, antimony, tungsten, and an alkaU metal. Process optimization continues to be in the form of incremental improvements in catalyst yield and lifetime. Typically, a dilute stream, 5—10% of isobutylene tert-huty alcohol) in steam (10%) and air, is passed over the catalyst at 300—420°C. Conversion is often nearly quantitative, with selectivities to methacrolein ranging from 85% to better than 95% (114—118). Often there is accompanying selectivity to methacrylic acid of an additional 2—5%. A patent by Mitsui Toatsu Chemicals reports selectivity to methacrolein of better than 97% at conversions of 98.7% for a yield of methacrolein of nearly 96% (119). 

A few industrial catalysts have simple compositions, but the typical catalyst is a complex composite made up of several components, illustrated schematically in Figure 9 by a catalyst for ethylene oxidation. Often it consists largely of a porous support or carrier, with the catalyticaHy active components dispersed on the support surface. For example, petroleum refining catalysts used for reforming of naphtha have about 1 wt% Pt and Re on the surface of a transition alumina such as y-Al203 that has a surface area of several hundred square meters per gram. The expensive metal is dispersed as minute particles or clusters so that a large fraction of the atoms are exposed at the surface and accessible to reactants (see Catalysts, supported). 

Dehalogenation of monochlorotoluenes can be readily effected with hydrogen and noble metal catalysts (34). Conversion of -chlorotoluene to Ncyanotoluene is accompHshed by reaction with tetraethyl ammonium cyanide and zero-valent Group (VIII) metal complexes, such as those of nickel or palladium (35). The reaction proceeds by initial oxidative addition of the aryl haHde to the zerovalent metal complex, followed by attack of cyanide ion on the metal and reductive elimination of the aryl cyanide. Methylstyrene is prepared from -chlorotoluene by a vinylation reaction using ethylene as the reagent and a catalyst derived from zinc, a triarylphosphine, and a nickel salt (36). 

The modes of thermal decomposition of the halates and their complex oxidation-reduction chemistry reflect the interplay of both thermodynamic and kinetic factors. On the one hand, thermodynamically feasible reactions may be sluggish, whilst, on the other, traces of catalyst may radically alter the course of the reaction. In general, for a given cation, thermal stability decreases in the sequence iodate > chlorate > bromate, but the mode and ease of decomposition can be substantially modified. For example, alkali metal chlorates decompose by disproportionation when fused ... 

Zinc-tartrate complexes were applied for reactions of both nitrones and nitrile oxides with allyl alcohol and for both reaction types selectivities of more than 90% ee were obtained. Whereas the reactions of nitrones required a stoichiometric amount of the catalyst the nitrile oxide reactions could be performed in the presence of 20 mol% of the catalyst. This is the only example on a metal-catalyzed asymmetric 1,3-dipolar cycloaddition of nitrile oxides. It should however be no-... 

Among the J ,J -DBFOX/Ph-transition(II) metal complex catalysts examined in nitrone cydoadditions, the anhydrous J ,J -DBFOX/Ph complex catalyst prepared from Ni(C104)2 or Fe(C104)2 provided equally excellent results. For example, in the presence of 10 mol% of the anhydrous nickel(II) complex catalyst R,R-DBFOX/Ph-Ni(C104)2, which was prepared in-situ from J ,J -DBFOX/Ph ligand, NiBr2, and 2 equimolar amounts of AgC104 in dichloromethane, the reaction of 3-crotonoyl-2-oxazolidinone with N-benzylidenemethylamine N-oxide at room temperature produced the 3,4-trans-isoxazolidine (63% yield) in near perfect endo selectivity (endo/exo=99 l) and enantioselectivity in favor for the 3S,4J ,5S enantiomer (>99% ee for the endo isomer. Scheme 7.21). The copper(II) perchlorate complex showed no catalytic activity, however, whereas the ytterbium(III) triflate complex led to the formation of racemic cycloadducts. 

So-called reverse ATRP has been described where a conventional radical initiator (e.g. AIBN) and a transition metal complex in its Higher oxidation state are used. 85"288 One of the first systems explored was ( uBr- 133 AIBN VI VIA. It is important that the initiator is completely consumed early in the polymerization. The use of peroxide initiators in reverse ATRP can be problematical depending on the catalyst used and the reaction temperature.286 289 The system CuBr2/133/BPO/MMA at 60°C was found to provide no control,286 In ATRP at lower temperatures (40 °C), the system CuCl/133/BPO/MMA was successful though dispersities obtained were relatively broadf89 Radicals are produced from the redox reaction between the catalyst in its reduced form and BPO. 

Transition metal catalysts arc characterized by their redox ehemistry (catalysts can be considered as one electron oxidants/reductants). They may also be categorized by their halogen affinity. While in the initial reports on ATRP (and in most subsequent work) copper266,267 or ruthenium complexes267 were used, a wide range of transition metal complexes have been used as catalysts in ATRP. 

Metal complexes of porphine and azaporphine compounds as catalysts of reactions involving oxidation of molecular oxygen. N. S. Enikolopyan, K. A. Bogdanova and K. A. Askarov, Russ. Chem. Rev. (Engl. Transl), 1983, 52,13-26 (161). 

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