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cataltic applications of metal carbonyls

cataltic applications of metal carbonyls

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data about metal carbonyls applications in catalysis
data about metal carbonyls applications in catalysis

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Published by: saud on Jun 05, 2008
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03/21/2012

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Catalytic Applications Of Metal Carbonyls
Catalysis
is the process by which the rate of a chemical reaction (or biological process) is increased by means of the addition of a species known as a
catalyst
to thereaction. What makes a catalyst different from a chemical reagent is that whilst it participates in thereaction, is not consumed in the reaction. That is, the catalyst may undergo several chemicaltransformations during the reaction, but at the conclusion of the reaction, the catalyst is regeneratedunchanged. As a catalyst is regenerated in a reaction, often only a very small amount is needed toincrease the rate of the reaction.
Overview 
A catalyst works by providing an alternative reaction pathway to the reaction product. The rate of thereaction is increased as this alternative route has a lower activation energythan the reaction route notmediated by the catalyst. The lower the activation energy, the faster the rate of the reaction.A real example is thedisproportionateof hydrogen peroxideto give water andoxygen:
2 H
2
O
2
→ 2 H
2
O + O
2
Whilst the above reaction is favoured in the sense that reaction products are more stable than the startingmaterial, the reaction is slow. This can be seen by the fact that hydrogen peroxide is often available for purchase on thehigh-streetin bottles as a disinfectant.However, upon the addition of a small amount of manganese dioxide, the hydrogen peroxide undergoes arapid reaction, which can be readily seen by theeffervescenceof oxygen.
[
]
The manganesedioxide may be recovered unchanged, and re-used indefinitely, and thus is not consumed in the reaction.Accordingly, manganese dioxide catalyses this reaction.In a more general sense, anything that increases the rate of any process is commonly called a "catalyst"(From theGreek καταλύειν,meaning
to annul 
or 
to untie
or 
to pick up
). For example amatchmaker mightbe called a catalyst, as he or she brings two people together who otherwise might not meet, with thematchmaker being unaltered by the matching process.The opposite of a catalyst is aninhibitor which slows the rate of a reaction without itself being consumed.
There are two types of catalysis:
1-Homogeneous Catalysis2-Heterogeneous Catalysis
Homogeneous Catalysis
Homogeneous catalysis is a chemistry term which describescatalysiswhere thecatalystis in the same phase (i.e. solid,liquidandgas) as thereactants. It is the opposite toheterogeneous catalysis.
 
Notice that two liquids can be different phases. Therefore, for example, the petrochemicalalkylation process featuresheterogeneous catalysis,although both the catalyst (acid) and reactants (hydrocarbons)are liquids .Thehydrolysisof estersbyacid catalysisis an example of this - all reactants and catalyst are dissolved in water:
CH3CO2CH3(aq) + H2O(l) ↔ CH3CO2H(aq) + CH3OH(aq) - with H+ catalyst.
Contemporary examples of homogeneous catalysis utilizing metal complexes includehydroformylation,Ziegler-Nattapolymerization,hydrogen transfer catalysis, hydrogenation, andC-H activation.
Heterogeneous catalysis
Heterogeneous catalysis is a 
 term which describes
 where the 
is in adifferent phase (i.e.
 and 
, but also
and
) to the 
.Heterogeneouscatalysts provide a surface for the chemical reaction to take place on. Here, the catalyst is often a solidwhereas the reactive phase is either a solution or a gas. This type of catalysis is extremely important inindustrial processes.The reagents are fixed on the surface of catalyst (often by non-covalent interactions);the newly created interactions weaken internal bonds, which makes them more reactive.In order for the reaction to occur, one or more of the reactants must
 to the catalyst surface and
onto it. After reaction, the products must desorb from the surface and diffuse away from the solidsurface. Frequently, this transport of reactants and products from one phase to another plays a dominantrole in limiting the
. Understanding these transport phenomena and
such as
is an important area of heterogeneous catalyst research. Catalystsurface area may also be considered. 
,for example, have found utility ascatalysts because their surface areas may be in excess of 1000 m2/g, which increases the probability thata reactant molecule in solution will come in contact with the catalyst surface and adsorb. If diffusion ratesare not taken into account, the reaction rates for various
depend solely on therate constants and reactant concentrations. Asymmetric heterogeneous catalysis can be used tosynthesize enantiomerically pure compounds using chiral heterogeneous catalysts.
Example :
transformation of a double C=C bond into simple bond
The reaction is catalysed by a surface of palladium adsorbed on carbon. The reaction occurs in threesteps: adsorption of the reagents (a and b below), transfer of the hydrogen atoms and desorption of theend product (c below).
 Applications
Industrial applications
Today catalysts are used in untold numbers of industrial processes. For example, the commerciallyimportant gas ammonia is produced by combining nitrogen gas and hydrogen gas at a high temperatureand pressure in the presence of a catalyst such as powdered iron. In the absence of the catalyst, thereaction between nitrogen and hydrogen would, for all practical purposes, not occur. In its presence, thereaction occurs quickly enough to produce ammonia gas in large quantities.
Application of new unsymmetrical chiral Mn(III), Co(II,III) and Ti(IV) salen complexes inenantioselective catalytic reactions
New unsymmetrical chiral salen complexes were synthesized and the efficiency of Mn(III), Ti(IV),Co(II) and Co(III) type catalysts were examined in the enantioselective epoxidation of styrene and α
methylstyrene, the trimethylsilylcyanation of benzaldehyde, the borohydride reduction of aromatic ketonesand asymmetric hydrolysis of epoxides to diols, respectively. A very high level of enantioselectivity wasattainable over the unsymmetrical chiral salen complexes prepared mainly from salicylaldehyde and 2

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