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 the
reaction. What makes a catalyst different from a chemical reagent is that whilst it participates in the
reaction, is not consumed in the reaction. That is, the catalyst may undergo several chemical
transformations during the reaction, but at the conclusion of the reaction, the catalyst is regenerated
unchanged. As a catalyst is regenerated in a reaction, often only a very small amount is needed to
increase the rate of the reaction.

Overview
A catalyst works by providing an alternative reaction pathway to the reaction product. The rate of the
reaction is increased as this alternative route has a lower activation energy than the reaction route not
mediated by the catalyst. The lower the activation energy, the faster the rate of the reaction.

A real example is the disproportionate of hydrogen peroxide to give water and oxygen:

2 H2O2 → 2 H2O + O2

Whilst the above reaction is favoured in the sense that reaction products are more stable than the starting
material, the reaction is slow. This can be seen by the fact that hydrogen peroxide is often available for
purchase on the high-street in bottles as a disinfectant.
However, upon the addition of a small amount of manganese dioxide, the hydrogen peroxide undergoes a
rapid reaction, which can be readily seen by the effervescence of oxygen.[citation needed] The manganese
dioxide 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 the Greek καταλύειν, meaning to annul or to untie or to pick up). For example a matchmaker might
be called a catalyst, as he or she brings two people together who otherwise might not meet, with the
matchmaker being unaltered by the matching process.
The opposite of a catalyst is an inhibitor which slows the rate of a reaction without itself being consumed.

There are two types of catalysis:

1- Homogeneous Catalysis

2- Heterogeneous Catalysis

Homogeneous Catalysis
Homogeneous catalysis is a chemistry term which describes catalysis where the catalyst is in the same
phase (i.e. solid, liquid and gas) as the reactants. It is the opposite to heterogeneous catalysis.
Notice that two liquids can be different phases. Therefore, for example, the petrochemical alkylation
process features heterogeneous catalysis, although both the catalyst (acid) and reactants (hydrocarbons)
are liquids .The hydrolysis of esters by acid catalysis is 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 include hydroformylation ,
Ziegler-Natta polymerization, hydrogen transfer catalysis, hydrogenation, and C-H activation.

Heterogeneous catalysis
Heterogeneous catalysis is a chemistry term which describes catalysis where the catalyst is in a
different phase (i.e. solid, liquid and gas, but also oil and water) to the reactants. Heterogeneous
catalysts provide a surface for the chemical reaction to take place on. Here, the catalyst is often a solid
whereas the reactive phase is either a solution or a gas. This type of catalysis is extremely important in
industrial 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 diffuse to the catalyst surface and
adsorb onto it. After reaction, the products must desorb from the surface and diffuse away from the solid
surface. Frequently, this transport of reactants and products from one phase to another plays a dominant
role in limiting the reaction rate. Understanding these transport phenomena and surface
chemistry such as dispersion is an important area of heterogeneous catalyst research. Catalyst
surface area may also be considered. Mesoporous silicates, for example, have found utility as
catalysts because their surface areas may be in excess of 1000 m2/g, which increases the probability that
a reactant molecule in solution will come in contact with the catalyst surface and adsorb. If diffusion rates
are not taken into account, the reaction rates for various reactions on surfaces depend solely on the
rate constants and reactant concentrations. Asymmetric heterogeneous catalysis can be used to
synthesize 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 three
steps: adsorption of the reagents (a and b below), transfer of the hydrogen atoms and desorption of the
end product (c below).

Applications

Industrial applications
Today catalysts are used in untold numbers of industrial processes. For example, the commercially
important gas ammonia is produced by combining nitrogen gas and hydrogen gas at a high temperature
and pressure in the presence of a catalyst such as powdered iron. In the absence of the catalyst, the
reaction between nitrogen and hydrogen would, for all practical purposes, not occur. In its presence, the
reaction 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 in
enantioselective 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 ketones
and asymmetric hydrolysis of epoxides to diols, respectively. A very high level of enantioselectivity was
attainable over the unsymmetrical chiral salen complexes prepared mainly from salicylaldehyde and 2‐
formyl‐4,6‐di‐tert‐butylphenol derivatives. Enantiomeric excess of the corresponding reaction product
obtained using unsymmetrical chiral salen catalysts was generally higher than that over conventional
symmetric chiral salen catalysts. Unsymmetrical chiral
salen - epoxidation - reduction - hydrolysis - trimethylsilylcyanation – enantioselectivity

The Divalent Titanium Complex Ti(O-i-Pr)4/2 i-PrMgX as an Efficient and

Practical Reagent for Fine Chemical Synthesis

This account describes synthetic transformations of unsaturated hydrocarbons, such as alkynes,

alkenes, and dienes, mediated by the divalent titanium reagent Ti(O-i-Pr)4/2 i-PrMgX, which proceed via (
2-alkene)- or ( 2-alkyne)-titanium intermediates. Many of these transformations are otherwise difficult
or require multi-step reaction sequences. Since Ti(O-i-Pr)4 and i-PrMgX are non-toxic and available in
bulk at low price, the reagent satisfies the qualifications for use in large-scale synthesis.

Catalytic Activation of Imine Derivatives Using Novel Lewis Acids

The Lewis acid-mediated reactions of imine are one of the most powerful methods for preparation
of nitrogen-containing compounds. However, there are few examples of the reactions using catalytic
amounts of Lewis acids, because the strong coordination of the products (which are mostly secondly or
tertiary amines), deactivates the acids. This article introduces several types of new achiral and chiral
Lewis acids which can mediated the reactions of imines catalytically. The essence of the catalytic
activation of imines by Lewis acids is the equilibrium between Lewis acids and bases (imines or
products), and it has been revealed that rare earth triflates (lanthanide and scandium
trifluoromethanesulfonate) are excellent catalysts for this purpose. Imino-aldol reactions, aza Diels-Alder
reactions, allylation reactions, cyanation reactions, and three-component reactions of aldehydes, amines,
and nucleophiles were successfully carried out in the presence of catalytic amounts of rare earth triflates.
Polymer-supported reagents also worked well by using the triflates as catalysts. In addition, it was shown
that group IV triflates (Zr and Hf triflates) were effective for catalytic activation of imines. The first truly
catalytic asymmetric reactions of imines have been achieved using new chiral Lewis acids. In the
presence of a catalytic amount of a chiral rare earth catalyst, imines derived from 2-aminophenol and
aldehydes reacted with cyclopentadiene or vinyl ethers to afford 8-hydroxytetrahydroquinoline derivatives
in high yields with high diastereo- and enantioselectivities. Moreover, the first catalytic enantioselective
Mannich-type reactions of imines with silyl enolates using a novel chiral zirconium catalyst have been
developed. High levels of enantioselectivities in the synthesis of chiral b-amino ester derivatives, b-amino
alcohol derivatives, and tetrahydropyridine derivatives have been achieved using these reactions.

Synthesis of polymeric salen complexes and application in the

enantioselective hydrolytic kinetic resolution of epoxides as catalysts

The polymeric (salen) Co(III) catalysts containing various counter anions have been synthesized,
and the asymmetric catalytic activities of these newly synthesized polymer-type salen complexes were
investigated in the HKR of terminal epoxides. The polymeric chiral salen Co(III) complexes catalyze the
hydrolysis of epichlorohydrine, 1,2-epoxybutane, 1,2-epoxyhexane and epoxystyrene with very high
enantioselectivities under mild conditions. The catalysts could be recovered and reused several times
without further treatment after reaction, showing no loss of activity and enantioselectivity.
Enzymes in Organic Synthesis: Application to the Problems of
Carbohydrate Recognition

Carbohydrates on cell surfaces are information molecules. Although only seven or eight
monosaccharides are commonly used as building blocks in mammalian systems, the multifunctionality of
these monomers can lead to the assembly of an immense variety of complex structures. Millions of
different tetrasaccharide structures, for example, can be constructed from this small number of building
blocks, if branching, the stereochemistry of glycosidic linkages, and the modification of hydroxyl and
amino groups are taken into consideration. Oligosaccharides therefore represent an effective class of
biomolecules that code for a vast amount of information required in various biological recognition
processes, such as intercellular communication, signal transduction, cell adhesion, infection, cell
differentiation, development and metastasis. The pace of development of pharmaceuticals based on
carbohydrates has, however, been slower than that based on other classes of biomolecules. Part of the
reason is the lack of technologies for the study of complex carbohydrates. There is no method to amplify
oligosaccharides for sequence analysis. There is no machine available for automated synthesis of
oligosaccharides. In addition, the possibly poor bioavailability and difficulties in the large-scale synthesis
of carbohydrates have undoubtedly contributed to this slow pace. The enzymatic and chemoenzymatic
methods, especially those based on aldolases and glycosyltransferases, described here appear to be
useful for the synthesis of mono- and oligosaccaharides and related molecules. Further advances in
glycobiology will probably lead to the development of new technologies for the study of carbohydrate
recognition and for the synthesis of bioactive carbohydrates and mimetics to control the recognition
processes.

Metal carbonyl cations in strong acids and their catalytic activities

Recent advances on metal carbonyl cations and their catalytic activities are reviewed and
discussed in relation to the property of M–CO bonding. In strong acids, the carbonyl cations of
monovalent copper, silver and gold catalyze the carbonylation of olefins, alcohols, dienes, diols,
aldehydes and saturated hydrocarbons at room temperature and atmospheric pressure to produce
tert-alkanoic acids in high yields.

Spectroscopic Characterization and Catalytic Application of

Copper(I), Silver(I) and Gold(I) Carbonyl Cations in Strong Acids

Detailed IR, Raman, and NMR spectroscopic characterization has been carried out on the group
11 metal carbonyl cations, Cu(CO)n+ (n = 1, 2, 3, 4), Ag(CO)n+ (n = 1, 2, 3), and Au(CO)n+ (n = 1, 2),
over a wide range of temperature and in a variety of strong acids. Based on these results their
molecular structures were determined and their stabilities are compared and discussed. The active
species have been determined to be Cu(CO)2+ (and Cu(CO)3+ as a minor species) instead of the
previously assigned Cu(CO)3+, Ag(CO)+ instead of the previously assigned Ag(CO)2+, and Au(CO)2+,
respectively, for the copper(I), silver(I) and gold(I) carbonyl cation-catalyzed carbonylation of olefins and
alcohols in concentrated sulfuric acid. The reaction mechanism previously proposed for the metal
carbonyl cation-catalyzed carbonylation has been modified to involve an olefin-metal-monocarbonyl (e.g.,
for Ag) or an olefin-metal-polycarbonyl (e.g., for Cu or Au) intermediate.
Asymmetric Cycloaddition Reactions Catalyzed by Transition Metal
Complexes

Cationic aqua complexes of a trans-chelating tridentate ligand, (R,R)-4,6-dibenzofurandiyl-2,2'-bis

(4-phenyloxazoline), and transition metal(II) perchlorates are effective catalysts in the cyclopentadiene
Diels-Alder reactions, nitrone cycloadditions, and diazomethane cycloadditions with 3-alkenoyl-2-
oxazolidinones to show excellent enantioselectivities. The active catalyst complex prepared from nickel(II)
perchlorate hexahydrate has an octahedral structure with three aqua ligands, and it can be isolated and
stored for months without loss of catalytic activity. The aqua complex prepared from Ni(II) or Zn(II)
perchlorate results in highly effective chiral amplification in the Diels-Alder reaction. Two mechanisms for
amplification are involved for this remarkable chiral amplification: (1) precipitation of S4-symmetric meso-
2:1 complex between DBFOX/Ph and Ni(II) ion, and (2) associative formation of 1:1 heterochiral
complexes by the aid of hydrogen bonds based on aqua ligands to produce stable meso oligomers.

Hypervalent Iodine Reagents for the Oxidation of Alcohols and Their Application
to Complex Molecule Synthesis

Hypervalent iodine(V) derivatives such as 2-iodoxybenzoic acid (IBX) and Dess-Martin

periodinane [DMP; 1,1,1-tris(acetyloxy)-1,1-dihydro-1,2-benziodoxol-3-(1H)-one] have been used widely
for the oxidation of alcohols to aldehydes and ketones during the last decade because of their high
chemoselectivity, mild reactivity, and high yielding process. This review focuses on the recent progress in
the oxidation of alcohols to carbonyl compounds using IBX, DMP, and other hypervalent iodine reagents,
and their application to total syntheses of a variety of complex natural products.

Transition metal-catalyzed asymmetric cycloaddition reactions of a chiral (β-sulfinyl)vinylcyclopropane

derivative: asymmetric synthesis of a cyclopentane derivative using a chiral sulfinyl functionality as the
chiral source
Asymmetric synthesis of a cyclopentane derivative using a chiral sulfinyl functionality as the chiral source
has been successfully executed by a transition metal-catalyzed asymmetric cycloaddition reaction of a
chiral (β-sulfinyl)vinylcyclopropane derivative with acrylonitrile. The effects of the catalysts, ligands, and
solvent were examined. The degree of the asymmetric induction and the chemical yield were highly
dependent on the catalyst and, especially, the ligand used. A plausible mechanism of the asymmetric
induction is proposed.
Coordination chemistry of 1,3,5-triaza-7-phosphaadamantane (PTA) Transition metal complexes and
related catalytic, medicinal and photoluminescent applications
The cage-like water-soluble monodentate phosphine 1,3,5-triaza-7-phosphaadamantane (PTA) has
received renewed interest in the recent literature due to its properties to solubilize transition metal
complexes in aqueous phase. This property has allowed application of Rh, Ru and Pd-PTA complexes in
aqueous phase or biphasic homogeneous catalysis, antitumoral tests (Ru- and Pt-PTA) and
photoluminescence (Au-PTA). This paper reviews the synthesis and structural properties of PTA and
derivatives, their transition metal complexes, catalytic, medicinal and photoluminescence uses.
Sulfonium Ylides. Application to the Synthesis of Optically Active Epoxides
The transfer of benzylidene groups from S-benzylsulfonium salts obtained from several optically active
thiolanes and thianes to aldehydes and ketones yields optically active epoxides with high enatiomeric
purity. In contrast, methylene transfer via the same auxiliaries leads to inactive epoxides. It is proposed
that the difference in behaviour between these systems is best explained by assuming a 2+2
cycloaddition mechanism rather than the more commonly proposed nucleophilic anti-periplanar addition
for the reaction of a sulfur ylide with a carbonyl component.
Synthesis of (Allyloxy)(alkynyl)carbene Complexes and Their Reaction with
Octacarbonyldicobalt

Pentacarbonyl[(allyloxy)((4-methylphenyl~eth~yl)carbenelchromiuamn d tungsten complexes 1

and 2 have been prepared in moderate yields from the corresponding metal hexacarbonyl in a two-step,
one-pot, Fischer type nucleophilidelectrophilic addition methodology using allyl triflate as alkylating
reagent. As a consequence of its pronounced electrophilicity it also attacks the solvent THF, which results
in the formation of the (((ally1oxy)butyl)oxy)carbene complex 3 as a byproduct. Both the alkene-alkyne
complexes 1 and 2 and their COZ(CO)Sad ducts fail to undergo intramolecular Pauson-Khand reactions;
instead, at room temperature, a l,2-elimination within the carbene ligand occurs, regenerating the metal
hexacarbonyl with predominant formation of the 1,4-enynes 4 and 8-10. This process corresponds to an
unprecedented an unprecedented retroversion of the customary Fischer carbine complex synthesis.

Fischer-type Carbene Complexes in Organic Synthesis

The addition reaction of organolithium or Grignard reagents to silyl-sbstituted Fischer-type carbene

complex gives either (E)- or (Z)-vinylsilanes with high selectivities depending on the reaction conditions.
A new type of propargyl metallic species is generated by the addition reaction of alkynyllithiums with
Fischer-type carbene complexes. These species act as regiochemically well-behaved propargyl metallic
species and react with various electrophiles to give five-membered heterocyclic compounds. This reaction
was applied to a concise enantioselective total synthesis of (-)- PI-091.
Variable temperature NMR studies of the reaction of the propargyl tungsten species with electrophiles
revealed that 1,2-migration of pentacarbonyltungsten occurs to generate a vinyl metallic species. Highly
efficient method was developed for the preparation of a variety of synthetically useful, fully substituted
five-membered heterocyclic compounds by the iodine-oxidation of the intermediates produced from
Fischer-type carbene complexes, alkynes, and various carbon electrophiles.

High Activation of Carbonyl Groups with Bidentate Lewis Acid

Catalysts

Carbonyl group is one of the most popular and yet ubiquitous functionality of organic compounds
and often encountered in biomolecules such as peptides and lipids, playing a crucial role to organize
three dimensional intermolecular associations. For organic chemists, it always appears as an extremely
useful functional group to be manipulated and either Bronsted acids or Lewis acids are routinely
employed for the activation of carbonyls in electrophilic substitution reactions, where the acids preferably
coordinate to one of the two carbonyl lone pairs. Being close to the core of Lewis acid chemistry, we have
been interested some time in the possibility of double electrophilic activation of carbonyl functionality by
designing bidentate Lewis acid catalysts which could simultaneously coordinate to both of the carbonyl
lone pairs with two metals. In this review, we describe the development of bidentate aluminum and
titanium Lewis acids, and evaluation of their reactivity and selectivity in organic synthesis. Further, the
applications of our concept to the elaboration of new
synthetic methodologies are also discussed. Those include neutral allylation of carbonyls with bidentate
tin compounds by using chelation-induced Lewis acidity, and activation of bidentate bis(silyl) compounds
with a fluoride anion.
Key words: Bidentate Lewis acid, Bis(aluminum) reagent, Carbonyl Group, Double activation,
Chemoselective, Bis(titanium) reagent, Bis(allyl)tin compound, Neutral allylation, Bis(allyl)silyl compound
Asymmetric Reactions Using Non-natural Chiral Auxiliaries

In recent years, the development of chiral auxiliaries has been attracting much attention. Although
many of these are usually derived from natural chiral compounds, limitations in their structural
modification are sometimes an obstacle to achieve an efficient asymmetric process. This problem would
be solved by using non-natural chiral compounds due to their two favorable characteristics in contrast to
natural products and their derivatives:

1) Both enantiomers are readily available and can be used in asymmetric reactions.

2)The structure can be freely designed.

In the preparation of well-designed, non-natural chiral auxiliaries, the optical resolution of their
racemic modifications is thought to be one of the most practical methods. In this context, the development
of an efficient method for the optical resolution of a racemic modification is considered to be essential. We
have been carrying out a study which was coherent with the design, optical resolution, and application of
non-natural chiral auxiliaries. In this review we would like to describe our recent results concerning the
development of new non-natural chiral auxiliaries as well as their application to asymmetric syntheses.

References :

➢ www.springerlink.com

➢ www.freshpatents.com/Photoactive-metal-nitrosyls-for-blood-pressure-regulation-and-cancer-
therapy-dt20051

➢ www.lavoisier.fr/notice/fr412570.html
➢ www.chemistry.ucsc.edu/projects/surf/SURF_2008_Application.pdf
➢ www.cobalt.chem.ucalgary.ca/ps/posters/EPR-FeP/FeNO-P-Poster.ppt
➢