INORGANIC CHEMISTRY III

(CHEM 4083)
UNIT 3
ORGANOMETALLIC CHEMISTRY
3.1 INTRODUCTION
Organometallic chemistry is the study of chemical compounds containing bonds between carbon and a
metal. Since many compounds without such bonds are chemically similar, an alternative may be
compounds containing metal-element bonds of a largely covalent character. Organometallic chemistry
combines aspects of inorganic chemistry and organic chemistry.
Organometallic compounds:
Organometallic compounds are distinguished by the prefix "organo-" e.g. organopalladium compounds.
Examples of such organometallic compounds include all Gilman reagents, which contain lithium and
copper, Tetracarbonylnickel, and ferrocene are examples of organometallic compounds containing
transition metals. Other examples include organo-magnesium compounds like iodo(methyl)magnesium
MeMgI, diethylmagnesium (Et2Mg), and all Grignard reagents; organolithium compounds such as nbutyllithium
(n-BuLi),
organozinc
compounds
such
as
diethylzinc
(Et2Zn)
and
chloro(ethoxycarbonylmethyl)zinc (ClZnCH2C(=O)OEt); and organocopper compounds such as lithium
dimethylcuprate (Li+[CuMe2]–).
The term "metalorganics" usually refers to metal-containing compounds lacking direct metal-carbon
bonds but which contain organic ligands. Metal beta-diketonates, alkoxides, and dialkylamides are
representative members of this class.
In addition to the traditional metals, lanthanides, actinides, and semimetals, elements such as boron, silicon,
arsenic, and selenium are considered to form organometallic compounds, e.g. organoborane compounds
such as triethylborane (Et3B).
Coordination compounds with organic ligands
Many complexes feature coordination bonds between a metal and organic ligands. The organic ligands
often bind the metal through a heteroatom such as oxygen or nitrogen, in which case such compounds are
considered coordination compounds. However, if any of the ligands form a direct M-C bond, then complex
is usually considered to be organometallic, e.g., [(C6H6)Ru(H2O)3]2+. Furthermore, many lipophilic
compounds such as metal acetylacetonates and metal alkoxides are called "metalorganics."
Many organic coordination compounds occur naturally. For example, hemoglobin and myoglobin contain
an iron center coordinated to the nitrogen atoms of a porphyrin ring; magnesium is the center of a chlorin
ring in chlorophyll. The field of such inorganic compounds is known as bioinorganic chemistry. In contrast
to these coordination compounds, methylcobalamin (a form of Vitamin B12), with a cobalt-methyl bond, is
a true organometallic complex, one of the few known in biology. These subsets of complexes are often
discussed within the subfield of bioorganometallic chemistry. Illustrative of the many functions of the B12dependent enzymes, the MTR enzyme catalyzes the transfer of a methyl group from a nitrogen on N5methyl-tetrahydrofolate to the sulfur of homocysteine to produce methionine.
The status of compounds in which the canonical anion has a delocalized structure in which the negative
charge is shared with an atom more electronegative than carbon, as in enolates, may vary with the nature of
the anionic moiety, the metal ion, and possibly the medium; in the absence of direct structural evidence for
a carbon–metal bond, such compounds are not considered to be organometallic.
3.1.1 Historical Background
Early developments in organometallic chemistry include Louis Claude Cadet’s synthesis of methyl arsenic
compounds related to cacodyl, William Christopher Zeise's platinum-ethylene complex, Edward
Frankland’s discovery of dimethyl zinc, Ludwig Mond’s discovery of Ni(CO)4, and Victor Grignard’s
organomagnesium compounds. The abundant and diverse products from coal and petroleum led to Ziegler-

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Natta, Fischer-Tropsch, hydroformylation catalysis which employs CO, H 2, and alkenes as feedstocks and
ligands.
Tetraethyllead previously was combined with gasoline as an antiknock agent. Due to lead's toxicity it is no
longer used, its replacements being other organometallic compounds such as ferrocene and
methylcyclopentadienyl manganese tricarbonyl (MMT).
Recognition of organometallic chemistry as a distinct subfield culminated in the Nobel Prizes to Ernst
Fischer and Geoffrey Wilkinson for work on metallocenes. In 2005, Yves Chauvin, Robert H. Grubbs and
Richard R. Schrock shared the Nobel Prize for metal-catalyzed olefin metathesis.
Organometallic chemistry timeline
3.1.2 Structure And Properties:
The metal-carbon bond in organometallic compounds is generally of character intermediate between ionic
and covalent. Primarily ionic metal-carbon bonds are encountered either when the metal is very
electropositive (as in the case of Group 1 or Group 2 metals) or when the carbon-containing ligand exists as
a stable carbanion. Carbanions can be stabilized by resonance (as in the case of the aromatic
cyclopentadienyl anion) or by the presence of electron-withdrawing substituents (as in the case of the
triphenylmethyl anion). Hence, the bonding in compounds like sodium acetylide and
triphenylmethylpotassium is primarily ionic. On the other hand, the ionic character of metal-carbon bonds
in the organometallic compounds of transition metals, poor metals, and metalloids tends to be intermediate,
owing to the middle-of-the-road electronegativity of such metals.
Organometallic compounds with bonds that have characters in between ionic and covalent are very
important in industry, as they are both relatively stable in solutions and relatively ionic to undergo
reactions. Two important classes are organolithium and Grignard reagents. In certain organometallic
compounds such as ferrocene or dibenzenechromium, the pi orbitals of the organic moiety ligate the metal.
The physical and chemical properties of organometallic compounds vary greatly. Most are solids,
particularly those whose hydrocarbon groups are ring-shaped or aromatic, but some are liquids and some
are gases. Their heat and oxidation stability vary widely. Some are very stable, but a number of compounds
of electropositive elements such as lithium, sodium, and aluminum are spontaneously flammable. Many
organometallic compounds are highly toxic, especially those that are volatile. The properties of the
organometallic compounds depend in large measure on the type of carbon-metal bonds involved. Some are
ordinary covalent bonds, in which pairs of electrons are shared between atoms. Others are multicentre
covalent bonds, in which the bonding involves more than two atoms. A third type is ionic bonds, in which
the bonding electron pair is donated by only one atom. In donor-acceptor bonds, the metal atom is
connected to hydrocarbons with multiple bonds between carbon atoms.
Where metal atoms form covalent bonds with carbon atoms, the electrons are usually shared unequally. As
a result, the bond is polarized—one end is more negative than the other. The extent of polarization depends
on the strength with which the metal atom binds electrons. Organometallic compounds range in polar
power from methy-lpotassium, in which the bond is almost like certain ionic bonds, to lead, which bonds
with carbon with very little polarization.
3.1.3 Classifications Of Organometallic Compounds By Bond Type
Organometallic compounds are classified into different type base on the nature of metal-carbon bond.
Organometallic compounds can form both ionic bonds with electropositive elements as well as covalent
bonds with several main group and d-block elements. The metal-carbon bond in organometallic compounds
is generally of character intermediate between ionic and covalent.
Primarily ionic metal-carbon bonds are encountered either when the metal is very electropositive (as in
the case of the alkali metals) or when the carbon-containing ligand exists as a stable carbanion. Carbanions
can be stabilized by resonance (as in the case of the aromatic cyclopentadienyl anion) or by the presence of
electron-withdrawing substituents (as in the case of the triphenylmethyl anion). Hence, the bonding in
compounds like sodium acetylide and triphenylmethylpotassium is primarily ionic. On the other hand, the

2

ionic character of metal-carbon bonds in the organometallic compounds of transition metals, poor metals,
and metalloids tends to be intermediate, owing to the middle-of-the-road electronegativity of such metals.
Organometallic compounds with bonds that have characters in between ionic and covalent are very
important in industry, as they are both relatively stable in solutions and relatively ionic to undergo
reactions. Two important classes are organolithium and Grignard reagents. In certain organometallic
compounds such as ferrocene or dibenzenechromium, the pi orbitals of the organic moiety ligate the
metal.
Metal-Carbon Bridge Bonding:
The light electropositive elements (e.g. Li,Be, Mg< Al) form organometallic compounds such as MeLi,
Me2Mg, Ph3Al etc. These compounds do not exist as monomers rather form oligomers, or polymers,
namely, (MeLi)4, (Me2Mg)n, Ph3Al)2 involving bridging by alkyl or aryl groups. This bridge formation is
similar to that I boranes which involve two electron-three center bonds. The metal-carbon bonds have
considerable covalent character.
Metal-Carbon Two Electron Covalent Bonds:
The main group elements form binary alkyls and arylis, MRm which have single two electron M-C bonds,
the polarity of which depends on their electronegativity differences. For example, Al-C bonds in Me0.0)
than B-C bonds in Me3Al are more polar (Xc- XAl = 2.5 – 1,6 = B (Xc-XB = 2.5 – 2.1 = 0.4). The M-C
bond strength decreases with increase in atomic number main group elements. This difference is due to
more effective overlap of carbon (2s/2p) orbitals with the metal in the same row, rather than with the metal
down the group, which has more diffuse s and p-orbitals. The alkyl and aryl derivatives of transition
elements with M-C bonds are also known; however their isolation and stability varies with the organic
group and nature of metal.
For instance, MeEt44 Ti has been isolated but is unstable and decomposes readily, while Ti is too unstable
to be isolated. This liability is not due to weakness of Ti-C bonds; rather it is attributed to kinetic
instability. The M-C bond strength among transition elements increases down the group, a trend opposite
to that observed in the main group elements. This explained as follows: The 3d orbitals (first transition
series) are more contracted than 4d (second transition serried) or 5d (third transition series) orbitals, and
thus M-C overlap increases in the order: 5d > 4d > 3d.
3.1.4 The ‘Stability’ And Reactivity Of Organometallics Compounds
The stability and reactivity of organometallic compounds are associated with the nature of the organic
ligands and the metal to which they are attached. Each of the main group of the periodic table (groups 1, 2,
and 13–15), the thermal stability of a given type of organometallic compound generally decreases from the
lightest to the heaviest element in a group. For example, in compounds containing group-1 metals,
methyllithium(LiCH3) much more stable than methyl potassium (KCH3)tetramethylsilicon, Si(CH3)4
tetramethyllead, Pb(CH3)4 ), and, in those with group-14 metals, , is stable in the absence of air at 500 °C
(932 °F), whereas , rapidly decomposes at that temperature. This trend in stability is a consequence in part
of the decrease in M-C bond strength on going down within a group. The trend does not hold for the dblock elements (groups 3–12), where M-Cbond strengths and stability often increase going down a group.
The reactivities of organometallic compounds with water and air vary widely. The highly active maingroup metals such as lithium (Li), sodium (Na), magnesium (Mg), and aluminum (Al) form highly air- and
water-sensitive organometallic compounds. For example, A methane Al2(CH3)6 undergoes immediate and
violent reaction with water to liberate ) gas, and it bursts immediately into flame contact with air. For the
elements toward the right of the periodic table (groups 14 and 15), the organometallic compounds are not
water-sensitive; tetramethylsilicon, for example, does not react with water or air at room temperature.
As in other areas of chemistry, electron counting is useful for organizing organ metallic chemistry. The 18electron rule is helpful in predicting the stabilities of organometalliccompounds and related
compounds. Chemical bonding and reactivity in organometallic compounds is often discussed from the
perspective of the isolobal principle.
NMR and infrared spectroscopy are common techniques used to determine structure. The dynamic
properties of organometallic compounds are often probed with variable-temperature NMR and chemical
kinetics.
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18 electron rule:

The effective atomic number (EAN) rule states that most stable organometallic complexes have 18
electrons surrounding the metal. This is also known as the 18-electron rule.
 Metals that contain 18 electrons around them are called coordinatively saturated.
 Metals that contain less than 18 electrons around them are called coordinatively unsaturated and have
vacant coordination sites.
 To determine whether or not a metal is coordinatively saturated, we need to know how many electrons
the ligand donates.
 There are two ways to count electrons: ionic and covalent
 Both give the same answer.
 Ionic counting assumes the metal is in a formal oxidation state and the ligands are charged.
 Covalent counting assumes the metal is in the zero oxidation state and the ligands are neutral.
 Consider these compounds; Cr(CO)6, Fe(CO)5 and Ni(CO)4, why they are different in number of CO
ligands? Answer: 18 electron rule.
Organometallic compounds will be most stable if they have 18 valence electrons in total.
This is an imporant empirical rule, i.e. the result of many observations and has no really sound justification
in theory.the best way to think is like the octate rulr-the transition metal is trying to attain the noble gas
configuration.
Transition metals have 9 valence orbitals-for the first row metals five 3d. One 4s and three 4p, which is
most stable if filled.
Since electrons come from both the metal and ligand, the 18 electron rule only applies to transition metal
organometallic compounds, generally with pi-acceptor ligands.
Most metal-metal bonds can be regarded as normal covalent bonds using one electron from each metal.
Example:
have a +1 charge to compensate for the one
negatively charged ligand. The +1 charge on the
metal is also its oxidation state.
So the Re is the in the +1 oxidation state. We
1) There is no overall charge on the complex
denote this in two different ways: Re(+1), Re(I),
2) There is one anionic ligand (CH3 , methyl
or ReI. I prefer the Re(+1) nomenclature because
group)
it is clearer. Most chemistry journals, however,
3) Since there is no overall charge on the
prefer the Roman numeral notation in parenthesis
complex (it is neutral), and since we have one
after the element.
anionic ligand present, the Re metal atom must
Now we can do our electron counting:

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Using the 18 Electron Rule
Count all the valence (outer) electrons) of the metal anf those donated to the metal by the ligands (usually 2
per lone pair).
Consider the following two carbonyl compounds:
Cr(CO)6: Cr has six valence electrons (e-) d6
6
6CO ligands→ 6x2 =
12e18
Ni(CO)4: Ni hsa ten valence electrons (e-)
10
4CO ligands→ 4x2 =
8e18

When there are an odd number of electrons, the species usually dimerses with the formation of M-M
bonds. Example;

5

3.2 Structure and bonding in organometallic compound
6

1. Metal-Carbon Ionic Bonds
The most electropositive elements like Na, K, etc from ionic organometallic compounds. For example, the
crystalline solid (close packed hexagonal) of methylpotassium (K+CH3) has isolated methyl anions (CH3)
and metal cations (K+).
Generally, the stability of anion is very important for the formation of ionic compounds. The stable anions
are encountered among aromatic rings and unsaturated organic groups, due to the possibility of
delocalization of anionic charge on the entire ring or unsaturated chain systems. In the formation of
sodium cyclopentadienyl salt (Na+C5H5), the radical (C5H5) readily accepts electron from Na atom to form
Caromatic ring system. Similarly, the anion of Na+ Ph 2C has aromatic ring system for delocalization of
electron accepted from Na atom. The negative charge in sodium ethynyl (Na+CH=C) is stabilized mainly
due to higher electronegativity of sp versus sp# hybridized carbon atoms. In all the examples cited above,
there is high degree of ionic character in M+R- compounds.
2. Metal-Carbon Bridge Bonding:
The light electropositive elements (e.g. Li,Be, Mg< Al) form organometallic compounds such as MeLi,
Me2Mg, Ph3Al etc. These compounds do not exist as monomers rather form oligomers, or polymers,
namely, (MeLi)4, (Me2Mg)n, Ph3Al)2involving bridging by alkyl or aryl groups. This bridge formation is
similar to that I boranes which involve two electron-three center bonds. The metal-carbon bonds have
considerable covalent character.
3. Metal-Carbon Two Electron Covalent Bonds:
The main group elements form binary alkyls and arylis, MRm which have single two electron M-C bonds,
the polarity of which depends on their electronegativity differences. For example, Al-C bonds in Me0.0)
than B-C bonds in Me3Al are more polar (Xc- XAl =2.5 – 1,6 = B (Xc-XB = 2.5 – 2.1 = 0.4). The M-C
bond strength decreases with increase in atomic number main group elements. This difference is due to
more effective overlap of carbon (2s/2p) orbitals with the metal in the same row, rather than with the metal
down the group, which has more diffuse s and p-orbitals.
The alkyl and aryl derivatives of transition elements with M-C bonds are also known; however their
isolation and stability varies with the organic group and nature of metal.
For instance, MeEt44Ti has been isolated but is unstable and decomposes readily, while
Ti is too unstable to be isolated. This liability is not due to weakness of Ti-C bonds; rather it is attributed to
kinetic instability. The M-C bond strength among transition elements increases down the group, a trend
opposite to that observed in the main group elements. This explained as follows: The 3d orbitals (first
transition series) are more contracted than 4d (second transition serried) or 5d (third transition series)
orbitals, and thus M-C overlap increases in the order: 5d > 4d > 3d.
4. Metal –Carbon Multiple Bonds
The multiple bond formation between carbon and other main group elements is uncommon. Phosphorus
and silicon form R3P=CH2 and R2C= SiR21 compounds. The latter however, do not exist as monomers,
rather form oligomers or polymers.
However, the use of bulky R/R1 group helps to prepare monomers. Multiple bonds are more common with
transition elements. Tungsten compounds of type, (OC) 5W=C(OMe)Me, and (Bu1O)3W=Cet, represent
some examples of the suitable metal d-orbitals and carbon 2p orbitals.
5. Metal-Carbon p-Bonds With Unsaturated Hydrocarbons
Organic compounds are known to form bonds via filled N electrons as for example, first observed in
ferrocene, and Zeise’s salt. It is essential that metal should have filled suitable which can form back-bonds
(N-bonds) to empty N+ orbitals centered on the organic ligand. A large number of n complexes have been
prepared with d-block elements, to a lesser extent with the lanthanides and actinides, and only small
number with main group elements.
Cyclopentadiene and cyclooctatetrtaene are some organic compounds which have formed a number of
complexes with various elements. The bonding is predominantly ionic in case of main group, polar in case
of f-block, and covalent in case of d-block elements
3.3Methods of formation of metal-carbon bonds
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3.1.1 Synthesis Of Main-Group Organometallics
There are many synthetic routes for the synthesis of main-group organometallics. Some are only used in a
laboratory setting because they are too costly for large-scale industrial use. On the other hand, many of the
industrial methods are difficult to implement in the laboratory because of the need for highly specialized
equipment and working conditions. The following reactions will serve as model equations for the common
synthetic routes:
a) Direct preparation; from a halocarbon (usually chloride or bromide) and the metallic element.
Preparation of organolithium compounds:
2 Li + RX → LiR + LiX
Preparation of Grignard reagents:
MgR X → RMgX
Rochow method for the production of methyl silylchlorides
This last reaction, uses a copper catalyst, and is an essential industrial process; without it the production
of silicones, an important class of synthetic hybrid inorganic/organic polymer not economical.
b) Transmetallation;
This is the displacement of one metal from a hydrocarbon group by another. The displacing metal must
be less electronegative than the displaced metal. Hence Hg, with the very high value of χ = 2.0 is
often used. This particular reaction is done at about 60°C in a sealed, shaken, heavy-wall glass reactor,
sometimes called a Carius tube).
c) Metathesis (which can, however, best be thought of as nucleophilic substitution.)
Li4 Me4 + SiCl4 → 4LiCl + SiMe
Al Me3 + 2BF3 → 2AlF3 + 2BMe
d) Redistribution reaction type (this is another form of metathesis, and here the label is highly
appropriate
SiCl4 + SiMe4
→SiClMe3 + SiCl Me3 + SiCl Me3 etc...
This reaction has considerable importance for the silicone industry, which is economically very
important.
e) Addition to a multiple bond;
Here E can be, e.g., BH2, SiH3, etThis is used extensively in organic chemistry in hydroboration for
antiMarkovnikovadditionto alkenes.[Organikersoxidize off the BH2 with H2O to make alcohols, and
with peroxybenzoic acid to make carboxylic acids.] A variation on this reaction is used industrially to
produce ethyl compounds by direct reaction of the metal and ethene in the presence of hydrogen gas.
This is a very important process for cheap large scale production of main-group organometallic
compounds.
3.4 Catalytic applications of organometallic compounds
Catalysis is the increase in rate of a chemical reaction due to the participation of a substance called a
catalyst. Unlike other reagents in the chemical reaction, a catalyst is not consumed. A catalyst may
participate in multiple chemical transformations. The effect of a catalyst may vary due to the presence of
other substances known as inhibitors or poisons (which reduce the catalytic activity) or promoters (which
increase the activity).
Catalyzed reactions have lower activation energy (rate-limiting free energy of activation) than the
corresponding uncatalyzed reaction, resulting in a higher reaction rate at the same temperature. However,
the mechanistic explanation of catalysis is complex. Catalysts may affect the reaction environment
favorably, or bind to the reagents to polarize bonds, e.g. acid catalysts for reactions of carbonyl compounds,
or form specific intermediates that are not produced naturally, such as osmate esters in osmium tetroxidecatalyzed dihydroxylation of alkenes, or cause dissociation of reagents to reactive forms, such as
chemisorbed hydrogen in catalytic hydrogenation.
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Kinetically, catalytic reactions are typical chemical reactions; i.e. the reaction rate depends on the
frequency of contact of the reactants in the rate-determining step. Usually, the catalyst participates in this
slowest step, and rates are limited by amount of catalyst and its "activity". In heterogeneous catalysis, the
diffusion of reagents to the surface and diffusion of products from the surface can be rate determining. A
nanomaterial-based catalyst is an example of a heterogeneous catalyst. Analogous events associated with
substrate binding and product dissociation apply to homogeneous catalysts.
Although catalysts are not consumed by the reaction itself, they may be inhibited, deactivated, or destroyed
by secondary processes. In heterogeneous catalysis, typical secondary processes include coking where the
catalyst becomes covered by polymeric side products. Additionally, heterogeneous catalysts can dissolve
into the solution in a solid–liquid system or evaporate in a solid–gas system.
The production of most industrially important chemicals involves catalysis. Similarly, most biochemically
significant processes are catalysed. Research into catalysis is a major field in applied science and involves
many areas of chemistry, notably in organometallic chemistry and materials science. Catalysis is relevant
to many aspects of environmental science, e.g. the catalytic converter in automobiles and the dynamics of
the ozone hole. Catalytic reactions are preferred in environmentally friendly green chemistry due to the
reduced amount of waste generated,[1] as opposed to stoichiometric reactions in which all reactants are
consumed and more side products are formed. The most common catalyst is the hydrogen ion (H +). Many
transition metals and transition metal complexes are used in catalysis as well. Catalysts called enzymes are
important in biology.
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 disproportionation of hydrogen peroxide creates water and oxygen, as shown
below.
2 H2O2 → 2 H2O + O2
This reaction is preferable in the sense that the reaction products are more stable than the starting material,
though the uncatalysed reaction is slow. In fact, the decomposition of hydrogen peroxide is so slow that
hydrogen peroxide solutions are commercially available. This reaction is strongly affected by catalysts such
as manganese dioxide, or the enzyme peroxidase in organisms. Upon the addition of a small amount of
manganese dioxide, the hydrogen peroxide reacts rapidly. This effect is readily seen by the effervescence of
oxygen. The manganese dioxide is not consumed in the reaction, and thus may be recovered unchanged
and re-used indefinitely. Therefore, manganese dioxide catalyses this reaction.
General principles
Typical mechanism
Catalysts generally react with one or more reactants to form intermediates that subsequently give the final
reaction product, in the process regenerating the catalyst. The following is a typical reaction scheme, where
C represents the catalyst, X and Y are reactants, and Z is the product of the reaction of X and Y:
X + C → XC (1)
Y + XC → XYC (2)
XYC → CZ (3)
CZ → C + Z (4)
Although the catalyst is consumed by reaction 1, it is subsequently produced by reaction 4, so for the
overall reaction:
X+Y→Z
As a catalyst is regenerated in a reaction, often only small amounts are needed to increase the rate of the
reaction. In practice, however, catalysts are sometimes consumed in secondary processes.
As an example of this process, in 2008 Danish researchers first revealed the sequence of events when
oxygen and hydrogen combine on the surface of titanium dioxide (TiO2, or titania) to produce water. With
a time-lapse series of scanning tunneling microscopy images, they determined the molecules undergo
adsorption, dissociation and diffusion before reacting. The intermediate reaction states were: HO2, H2O2,
then H3O2 and the final reaction product (water molecule dimers), after which the water molecule desorbs
from the catalyst surface.[4][5]
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Reaction energetics

Generic potential energy diagram showing the effect of a catalyst in a hypothetical exothermic chemical
reaction X + Y to give Z. The presence of the catalyst opens a different reaction pathway (shown in red)
with lower activation energy. The final result and the overall thermodynamics are the same.
Catalysts work by providing an (alternative) mechanism involving a different transition state and lower
activation energy. Consequently, more molecular collisions have the energy needed to reach the transition
state. Hence, catalysts can enable reactions that would otherwise be blocked or slowed by a kinetic barrier.
The catalyst may increase reaction rate or selectivity, or enable the reaction at lower temperatures. This
effect can be illustrated with a Boltzmann distribution and energy profile diagram.
In the catalyzed elementary reaction, catalysts do not change the extent of a reaction: they have no effect
on the chemical equilibrium of a reaction because the rate of both the forward and the reverse reaction are
both affected (see also thermodynamics). The fact that a catalyst does not change the equilibrium is a
consequence of the second law of thermodynamics. Suppose there was such a catalyst that shifted
equilibrium. Introducing the catalyst to the system would result in reaction to move to the new equilibrium,
producing energy. Production of energy is a necessary result since reactions are spontaneous if and only if
Gibbs free energy is produced, and if there is no energy barrier, there is no need for a catalyst. Then,
removing the catalyst would also result in reaction, producing energy; i.e. the addition and its reverse
process, removal, would both produce energy. Thus, a catalyst that could change the equilibrium would be
a perpetual motion machine, a contradiction to the laws of thermodynamics.
If a catalyst does change the equilibrium, then it must be consumed as the reaction proceeds, and thus it is
also a reactant. Illustrative is the base-catalysed hydrolysis of esters, where the produced carboxylic acid
immediately reacts with the base catalyst and thus the reaction equilibrium is shifted towards hydrolysis.
The SI derived unit for measuring the catalytic activity of a catalyst is the katal, which is a mole per
second. The productivity of a catalyst can be described by the turn over number (or TON) and the catalytic
activity by the turn over frequency (TOF), which is the TON per time unit. The biochemical equivalent is
the enzyme unit. For more information on the efficiency of enzymatic catalysis, see the article on Enzymes.
The catalyst stabilizes the transition state more than it stabilizes the starting material. It decreases the
kinetic barrier by decreasing the difference in energy between starting material and transition state. It does
not change the energy difference between starting materials and products (thermodynamic barrier), or the
available energy (this is provided by the environment as heat or light).
Materials
The chemical nature of catalysts is as diverse as catalysis itself, although some generalizations can be
made. Proton acids are probably the most widely used catalysts, especially for the many reactions
involving water, including hydrolysis and its reverse. Multifunctional solids often are catalytically active,
e.g. zeolites, alumina, higher-order oxides, graphitic carbon, nanoparticles, nanodots, and facets of bulk
materials. Transition metals are often used to catalyze redox reactions (oxidation, hydrogenation).
Examples are nickel, such as Raney nickel for hydrogenation, and vanadium(V) oxide for oxidation of
sulfur dioxide into sulfur trioxide. Many catalytic processes, especially those used in organic synthesis,
require so called "late transition metals", which include palladium, platinum, gold, ruthenium, rhodium,
and iridium.
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Some so-called catalysts are really precatalysts. Precatalysts convert to catalysts in the reaction. For
example, Wilkinson's catalyst RhCl(PPh3)3 loses one triphenylphosphine ligand before entering the true
catalytic cycle. Precatalysts are easier to store but are easily activated in situ. Because of this preactivation
step, many catalytic reactions involve an induction period.
Chemical species that improve catalytic activity are called co-catalysts (cocatalysts) or promotors in
cooperative catalysis.
Types of catalysts
Catalysts can be heterogeneous or homogeneous, depending on whether a catalyst exists in the same phase
as the substrate. Biocatalysts (enzymes) are often seen as a separate group.
Heterogeneous catalysts

Zeolites are extruded as pellets for easy handling in
catalytic reactors.

The microporous molecular structure of the zeolite
ZSM-5 is exploited in catalysts used in refineries
Heterogeneous catalysts act in a different phase than the reactants. Most heterogeneous catalysts are solids
that act on substrates in a liquid or gaseous reaction mixture. Diverse mechanisms for reactions on surfaces
are known, depending on how the adsorption takes place (Langmuir-Hinshelwood, Eley-Rideal, and Marsvan Krevelen). The total surface area of solid has an important effect on the reaction rate. The smaller the
catalyst particle size, the larger the surface area for a given mass of particles.
For example, in the Haber process, finely divided iron serves as a catalyst for the synthesis of ammonia
from nitrogen and hydrogen. The reacting gases adsorb onto "active sites" on the iron particles. Once
adsorbed, the bonds within the reacting molecules are weakened, and new bonds between the resulting
fragments form in part due to their close proximity. In this way the particularly strong triple bond in
nitrogen is weakened and the hydrogen and nitrogen atoms combine faster than would be the case in the
gas phase, so the rate of reaction increases. Another place where a heterogeneous catalyst is applied is in
the contact process (oxidation of sulfur dioxide on vanadium(V) oxide for the production of sulfuric acid).
Heterogeneous catalysts are typically “supported,” which means that the catalyst is dispersed on a second
material that enhances the effectiveness or minimizes their cost. Sometimes the support is merely a surface
on which the catalyst is spread to increase the surface area. More often, the support and the catalyst
interact, affecting the catalytic reaction. Supports are porous materials with a high surface area, most
commonly alumina or various kinds of activated carbon. Specialized supports include silicon dioxide,
titanium dioxide, calcium carbonate, and barium sulfate.
Electrocatalysts
In the context of electrochemistry, specifically in fuel cell engineering, various metal-containing catalysts
are used to enhance the rates of the half reactions that comprise the fuel cell. One common type of fuel cell
electrocatalyst is based upon nanoparticles of platinum that are supported on slightly larger carbon
particles. When in contact with one of the electrodes in a fuel cell, this platinum increases the rate of
oxygen reduction either to water, or to hydroxide or hydrogen peroxide.
Homogeneous catalysts
Homogeneous catalysts function in the same phase as the reactants, but the mechanistic principles invoked
in heterogeneous catalysis are generally applicable. Typically homogeneous catalysts are dissolved in a
solvent with the substrates. One example of homogeneous catalysis involves the influence of H+ on the
esterification of carboxylic acids, such as the formation of methyl acetate from acetic acid and methanol.[8]
For inorganic chemists, homogeneous catalysis is often synonymous with organometallic catalysts.
Organocatalysis

11

Whereas transition metals sometimes attract most of the attention in the study of catalysis, small organic
molecules without metals can also exhibit catalytic properties, as is apparent from the fact that many
enzymes lack transition metals. Typically, organic catalysts require a higher loading (amount of catalyst per
unit amount of reactant, expressed in mol% amount of substance) than transition metal(-ion)-based
catalysts, but these catalysts are usually commercially available in bulk, helping to reduce costs. In the
early 2000s, these organocatalysts were considered "new generation" and are competitive to traditional
metal(-ion)-containing catalysts. Organocatalysts are supposed to operate akin to metal-free enzymes
utilizing, e.g., non-covalent interactions such as hydrogen bonding. The discipline organocatalysis is
divided in the application of covalent (e.g., proline, DMAP) and non-covalent (e.g., thiourea
organocatalysis) organocatalysts referring to the preferred catalyst-substrate binding and interaction,
respectively.
Significance

Left: Partially caramelised cube sugar, Right: burning cube sugar with ash as catalyst
Estimates are that 90% of all commercially produced chemical products involve catalysts at some stage in
the process of their manufacture.[10] In 2005, catalytic processes generated about $900 billion in products
worldwide.[11] Catalysis is so pervasive that subareas are not readily classified. Some areas of particular
concentration are surveyed below.
Energy processing
Petroleum refining makes intensive use of catalysis for alkylation, catalytic cracking (breaking long-chain
hydrocarbons into smaller pieces), naphtha reforming and steam reforming (conversion of hydrocarbons
into synthesis gas). Even the exhaust from the burning of fossil fuels is treated via catalysis: Catalytic
converters, typically composed of platinum and rhodium, break down some of the more harmful
byproducts of automobile exhaust.
2 CO + 2 NO → 2 CO2 + N2
With regard to synthetic fuels, an old but still important process is the Fischer-Tropsch synthesis of
hydrocarbons from synthesis gas, which itself is processed via water-gas shift reactions, catalysed by iron.
Biodiesel and related biofuels require processing via both inorganic and biocatalysts.
Fuel cells rely on catalysts for both the anodic and cathodic reactions.
Catalytic heaters generate flameless heat from a supply of combustible fuel.
Bulk chemicals
Some of the largest-scale chemicals are produced via catalytic oxidation, often using oxygen. Examples
include nitric acid (from ammonia), sulfuric acid (from sulfur dioxide to sulfur trioxide by the chamber
process), terephthalic acid from p-xylene, and acrylonitrile from propane and ammonia.
Many other chemical products are generated by large-scale reduction, often via hydrogenation. The largestscale example is ammonia, which is prepared via the Haber process from nitrogen. Methanol is prepared
from carbon monoxide.
Bulk polymers derived from ethylene and propylene are often prepared via Ziegler-Natta catalysis.
Polyesters, polyamides, and isocyanates are derived via acid-base catalysis. Most carbonylation processes
require metal catalysts, examples include the Monsanto acetic acid process and hydroformylation.
Fine chemicals
Many fine chemicals are prepared via catalysis; methods include those of heavy industry as well as more
specialized processes that would be prohibitively expensive on a large scale. Examples include olefin
metathesis using Grubbs' catalyst, the Heck reaction, and Friedel-Crafts reactions.
Because most bioactive compounds are chiral, many pharmaceuticals are produced by enantioselective
catalysis (catalytic asymmetric synthesis).
Food processing

12

One of the most obvious applications of catalysis is the hydrogenation (reaction with hydrogen gas) of fats
using nickel catalyst to produce margarine. Many other foodstuffs are prepared via biocatalysis (see
below).
Biology; Main article: Biocatalysis
In nature, enzymes are catalysts in metabolism and catabolism. Most biocatalysts are protein-based, i.e.
enzymes, but other classes of biomolecules also exhibit catalytic properties including ribozymes, and
synthetic deoxyribozymes.
Biocatalysts can be thought of as intermediate between homogenous and heterogeneous catalysts, although
strictly speaking soluble enzymes are homogeneous catalysts and membrane-bound enzymes are
heterogeneous. Several factors affect the activity of enzymes (and other catalysts) including temperature,
pH, and concentration of enzyme, substrate, and products. A particularly important reagent in enzymatic
reactions is water, which is the product of many bond-forming reactions and a reactant in many bondbreaking processes.
Enzymes are employed to prepare many commodity chemicals including high-fructose corn syrup and
acrylamide.
Environment
Catalysis impacts the environment by increasing the efficiency of industrial processes, but catalysis also
plays a direct role in the environment. A notable example is the catalytic role of chlorine free radicals in the
breakdown of ozone. These radicals are formed by the action of ultraviolet radiation on
chlorofluorocarbons (CFCs).
Cl· + O3 → ClO· + O2
ClO· + O· → Cl· + O2
History
In a general sense, anything that increases the rate of a process is a "catalyst", a term derived from Greek
καταλύειν, meaning "to annul," or "to untie," or "to pick up." The term catalysis was coined by Jöns Jakob
Berzelius in 1835 to describe reactions that are accelerated by substances that remain unchanged after the
reaction. Other early chemists involved in catalysis were Eilhard Mitscherlich who referred to contact
processes and Johann Wolfgang Döbereiner who spoke of contact action and whose lighter based on
hydrogen and a platinum sponge became a huge commercial success in the 1820s. Humphry Davy
discovered the use of platinum in catalysis. In the 1880s, Wilhelm Ostwald at Leipzig University started a
systematic investigation into reactions that were catalyzed by the presence of acids and bases, and found
that chemical reactions occur at finite rates and that these rates can be used to determine the strengths of
acids and bases. For this work, Ostwald was awarded the 1909 Nobel Prize in Chemistry.
Catalysis is a process in which the rate of a reaction is enhanced by a relatively small amount of a different
substance (catalyst) that does not undergo any permanent change itself.
After one cycle the catalyst has to reach the same state as before the reaction.
• Opposed to surface reaction or stoichiometric reaction with acoreactant.
• Catalysts reduce the energy, which is necessary to proceedalong the reaction pathway.
• Catalysts offer new reaction pathways.
• Catalysts concentrate the reactants at the surface.
Organometallics find practical uses in stoichiometric and catalytic processes, especially processes
involving carbon monoxide and alkene-derived polymers. All the world's polyethylene and polypropylene
are produced via organometallic catalysts, usually heterogeneously via Ziegler-Natta catalysis. Acetic acid
is produced via metal carbonyl catalysts in the Monsanto process and Cativa process. Most synthetic
aldehydes are produced via hydroformylation. The bulk of the synthetic alcohols, at least those larger than
ethanol, are produced by hydrogenation of hydroformylation derived aldehydes. Similarly, the Wacker
process is used in the oxidation of ethylene to acetaldehyde.
Organolithium, organomagnesium, and organoaluminium compounds are highly basic and highly reducing.
They catalyze many polymerization reactions, but are also useful stoichiometrically.
III-V semiconductors are produced from trimethylgallium, trimethylindium, trimethylaluminum and related
nitrogen / phosphorus / arsenic / antimony compounds. These volatile compounds are decomposed along
13

with ammonia, arsine, phosphine and related hydrides on a heated substrate via metalorganic vapor phase
epitaxy (MOVPE) process for applications such as light emitting diodes (LEDs) fabrication.
Organometallic compounds may be found in the environment and some, such as organo-lead and organo
mercury compounds are a toxic hazard.
Concepts and techniques
As in other areas of chemistry, electron counting is useful for organizing organometallic chemistry. The 18electron rule is helpful in predicting the stabilities of metal carbonyls and related compounds. Chemical
bonding and reactivity in organometallic compounds is often discussed from the perspective of the isolobal
principle.
NMR and infrared spectroscopy are common techniques used to determine structure. The dynamic
properties of organometallic compounds are often probed with variable-temperature NMR and chemical
kinetics.
Organometallic compounds undergo several important reactions:
Oxidative addition and reductive elimination
 transmetalation
 organometallic substitution reaction
 carbometalation
 carbon-hydrogen bond activation
 Hydrometalation
 cyclometalation
 electron transfer
 Migratory insertion
 beta-hydride elimination
 Nucleophilic abstraction

14














READ ABOUT THE ABOVE REACTIONS!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!

 Organometallic Questions
1. Which of the following are organometallic reagents?
A. CH3CH2ONa
B. CH3CH2Li
C. CH3CH2BH2
D. (CH3CH2)2Zn
E. CH3CH2MgBr
F. CH3C≡CH
2. Which of the following "pictures" best represents the polarity of organometallic compounds?
A. R M
B. R+ MC. R- M+
3. Arrange the following in order of basicity, most basic to least basic.
 CH3CH2O-, CH3CH2-, CH2=CH-, CH3C≡C-, CH3CH2OH
4. What are the main products of the reaction of each of the following with ethyl magnesium
bromide followed by a regular acidic work-up?
 (A) CH3CH2CHO
 (B) C6H5CHO (Benzaldehyde)
 (C) CH3COCH3 (Propanone)
 (D) D2O
 (E) C6H5CO2CH3
 (F) C6H5CO2H
 (G) CH3CH2OH
 (H) CH3CH2Br
5. How would you prepare diphenyl lithium cuprate?

6. Which of the following "pictures" best represents the polarity of organometallic
compounds ?
 (a) C6H5Li
 (b) C6H5MgI
 (c) (C6H5)2LiCu
 (d) (C6H5)2Zn
7. Try using retrosynthesis to plan an efficient synthesis based on Grignard reactions
for the following from bromobenzene and any necessary organic or inorganic
reagents.
 (A) 1-Phenylethanol
 (B) Diphenylmethanol
 (C) Benzyl Bromide
 (D) 2-Phenylpropene

Organometallic Answers


Q

Remember, organometallic compounds contain carbon-metal bonds

(a) CH3CH2ONa : No, since it is an oxygen-metal bond
(b) CH3CH2Li : Yes there is a carbon-metal bond
(c) CH3CH2BH2 : No, boron is a non-metal
(d) (CH3CH2)2Zn : Yes there are 2 carbon-metal bonds
(e) CH3CH2MgBr : Yes there is a carbon-metal bond
(f) CH3C≡CNa : Yes there is a carbon-metal bond



Q



Q




Q

(c) Metals are electropositive and carbon is electronegative with respect to a metal.

CH3CH2- > CH2=CH- > CH3C≡C- > CH3CH2O- > CH3CH2OH

(check pKa's)

A good way to think of basicity is the ability of the basic atom to donate it's pair of electrons
(Lewis definition).
Factors such as electronegativity and hybridisation are important. Electronegative atoms are
poor electron donors since they hold onto their electrons. sp orbitals are more
electronegative then sp2 due to the higher "s" character. Likewise for sp2 over sp3.

The Grignard reagent CH3CH2MgBr gives the following products:

(a) 3-pentanol, CH3CH2CHOHCH2CH3

(b) 1-phenyl-1-propanol,
C6H5CHOHCH2CH3

(c) 2-methyl-2-butanol,
(CH3)2COHCH2CH3

(d) deuteroethane, CH3CH2D (due to
acidic D)

(e) 3-phenyl-3-pentanol,
C6H5COH(CH2CH3)2

(f) ethane, CH3CH3(due to acidic H)

(g) ethane, CH3CH3(due to acidic H)

(h) no useful reaction



Q


Cuprates are prepared by adding Cu (I) halides to organolithium reagents, so we must first
prepare the organolithium reagent.




Q


The cuprate (c) is the best choice. Organolithiums and Grignard reagents are too basic for
coupling reactions for alkane synthesis. Organozinc reagents are not reactive enough.

Qu 7: Which statement about organometallic compounds is false?

organometallics contain metal-carbon bonds.

the metal-carbon bond is highly polarized.

they are important sources of carbon nucleophiles.

they are important sources of carbon electrophiles.

they are used to form new carbon-carbon bonds.



Q






(a) CH3CH2ONa
(c) CH3CH2BH2
(e) CH3CH2MgBr

(b) CH3CH2Li
(d) (CH3CH2)2Zn
(f) CH3C≡CNa






Q



(b) R+ M-

(c) R- M+


Arrange the following in order of basicity, most basic to least basic.


(a) R M

CH3CH2O-, CH3CH2-, CH2=CH-, CH3C≡C-, CH3CH2OH


Q

What are the main products of the reaction of each of the following with ethyl
magnesium bromide followed by a regular acidic work-up ?




(a) CH3CH2CHO
(c) CH3COCH3 (propanone)
(e) C6H5CO2CH3
(g) CH3CH2OH




(b) C6H5CHO (benzaldehyde)
(d) D2O
(f) C6H5CO2H
(h) CH3CH2Br



Q

How would you prepare diphenyl lithium cuprate ?


Q

Which of the following reagents is best suited to preparing 1-phenylbutane from 1bromobutane ?

(a) C6H5Li


Q

(b) C6H5MgI

(c) (C6H5)2LiCu

(d) (C6H5)2Zn


 Try using retrosynthesis to plan an efficient synthesis based on Grignard reactions
for the following from bromobenzene and any necessary organic or inorganic
reagents.
 (a) 1-phenylethanol
 (b) diphenylmethanol

(c) benzyl bromide


(d) 2-phenylpropene