Metal Carbonyls

Assignment#1
Applications of Metal Carbonyls & their derivatives
Submitted by : Alsha Mehwish
Msc Chemistry III

Applications of Metal Carbonyls & their derivatives Roll# 20012507-001
Assignment #1
Course title: Inorganic chemistry-V
Course Code: CHEM-402 (Fall 2021)
Submitted by: ALSHA MEHWISH
Class: Msc Chemistry-III
Department : Chemistry
Submission date: Jan 10,2022
Page | 1
Table of Contents:
Contents Page#
INTRODUCTION………………………………………………………………………………. 3
APPLICATIONS OF METAL CARBONYL’S DERIVATIVES……………………………. 3
Ni(CO)4, Nickel tetracarbonyl………………………………………………………………………………………. 4
Cr(CO)6, Chromium hexacarbonyl…………………………………………………………………………………. 4
Fe3(CO)12, Triiron dodecacarbonyl…………………………………………………………………………………. 5
FLUOROCARBON DERIVATIVES OF METAL CARBONYLS…………………………. 6
CATALYTIC ACTIVITY OF METAL CARBONYLS……………………………………… 8
APPLICATION OF METAL CARBONYL CATIONS TO CATALYTIC REACTIONS.12
APPLICATIONS OF METAL CARBONYL AS REAGENTS IN SYNTHESIS…………. 14
USES OF METAL CARBONYLS……………………………………………………………. 19
REFERENCES……………………………………………………………………………………. 21
Page | 2
Metal Carbonyls
Introduction:
The coordination complexes of transition metals with carbon monoxide ligands is
called metal carbonyl. Metal carbonyls of transition elements constitute another
important class of organometallic compounds (compounds having at least one bond
between carbon and metal).
All d-block elements which contain only carbonyl ligands are called homoleptic
carbonyls. Lone pair of electrons are available on both carbon and oxygen atoms of
carbon monoxide ligand. However, the carbon atoms donate electrons to the metal,
these complexes are known as carbonyls. One of the most important π- acceptor
ligand is carbon monoxide.
Applications Of Metal carbonyl’s derivatives:

Metal carbonyl complexes are of great interest last 10 years and many people studies
have been done on these molecules. The successful development on the metal
carbonyl and their products has demonstrated by the various examples of the recent
literature.
The metal carbonyl complexes are usually stabilized by the metal centers in the low
oxidation states. Metal carbonyls are used in a number of industrially important
carbonylation reactions.
Page | 3
Ni(CO)4, Nickel tetracarbonyl:

Uses:
Since Ni(CO)4, on heating, decomposes to metallic nickel, it is used in the
production of nickel by Mond’s process.
➢ It is used for plating nickel on other metals.

➢ It is used as a catalyst for synthesis of acrylic monomers in plastic industries.
Cr(CO)6, Chromium hexacarbonyl:

An indirect method of preparation involves an action of carbon monoxide on a
mixture of Grignard reagent and anhydrous chromium chloride in ether which is
followed by decomposition with an acid to give chromium hexacarbonyl.
35−70atm
𝐶6 H5 MgBr + CrCl3 + CO ⟶ Cr(CO)2 (C6 H5 )4 + MgBrCl + MgBr2
𝐶r(CO)2 (C6 H5 )4 + 6H + → Cr(CO)6 + 2Cr +3 + 12(C6 H5 )− + 3H2
Uses:
➢ It reacts with sodium metal in liquid ammonia to give carbonylate anion.

liquid NH3
Cr(CO)6 + 2Na ⟶ Na2 + [Cr 2− (CO)5 ]2− + CO
➢ It gives substitution reactions with amines like en and py. At higher

temperatures (>150o C) several pyridyl derivatives are formed.
Page | 4
Cr(CO)6 + 2py → Cr(CO)4 (py)2 + 2C

Yellowish brown
2Cr(CO)6 + 5py → Cr2 (CO)7 (py)5 + 5CO
Orange
Cr(CO)6 + 3py → Cr(CO)3 (py)3 + 3CO
Bright red
Fe3(CO)12, Triiron dodecacarbonyl:

It is prepared by heating diiron nonacarbonyl dissolved in toluene.
70∘ C, Toluene
3Fe2 (CO)9 ⟶ 3Fe(CO)5 + (CO)12
Uses:
It gives substitution reaction with pyridine and methanol.
3Fe3 (CO)12 + 3py → Fe3 (CO)9 (py)3 + 3Fe(CO)5

2Fe3 (CO)12 + 3CH3 OH → Fe3 (CO)9 (CH3 OH)3 + 3Fe(CO)5
It reacts with sodium metal in ammonia to give carbonylate anion.

liquid NH3
Fe3 (CO)12 + 6Na ⟶ 3Na+2 [Fe2− (CO)4 ]2−
It reacts with nitric oxide to form iron dicarbonyl dinitrosyl.
85∘ C
Fe3 (CO)12 + 6NO ⟶ 3Fe(CO)2 (NO)2 + 6CO
Page | 5
Fluorocarbon Derivatives of Metal Carbonyls:

Metal carbonyl anions are sometimes useful for the preparation of fluorocarbon
derivatives of metal carbonyls.
However, reactions of metal carbonyl anions with perfluoroalkyl iodides do not yield
perfluoroalkyl metal carbonyl derivatives but instead yield metal carbonyl iodides,
e.g
NaMn(CO)3 + C2 F3 I ⟶ THFu (CO)E I + NaF + CF2 = CF2
The difference in the behavior of perfluoroalkyl iodides and that of nonfluorinated

alkyl iodides is a consequence of the large cumulative inductive effect of the multiple
fluorine atoms which makes the carbon atom of the carbon-iodine bond negative
relative to the iodine atom.
Sometimes perfluoroalkyl iodides are useful as mild reagents for the conversion of
metal carbonyl anions to the corresponding metal carbonyl iodides.
A two-step procedure involving decarbonylation of the corresponding

perfluoroacyl intermediate is effective in converting metal carbonyl anions to their
periluoroalkyl derivatives.
This procedure is similar to that discussed above for the preparation of vinyl and
phenylmetal carbonyl derivatives and is exemplified by the following preparations
of perfluoroalkyl metal carbonyl derivatives.
Page | 6
THF
NaMn(CO)5 + (CF8 OO)2 O ⟶ CF3 COMn(CO)5 + CF3 CO2 Na
Δ
CF3 COMn(CO)5 ⟶ CF2 Mn(CO)5 + CO
NaFe(CO)2 C2 H5 + C2 F8 COCl ⟶
C2 F6 COFe(CO)2 C3 H5 + NaCl
C2 F3 COFe(CO)2 C3 H3 ⟶ C2 F5 Fe(CO)2 C3 H3 + CO
hexane
2N2 Mn(OO)2 + ClCOCF2 CF2 CF3 COCl THF

(CO)4 MnCOCF2 CF2 CF2 COM(n(CO)2 + 2NaCl
10𝑠 ∘
(CO)𝑠 MnCOCF2 CF2 CF2 COMn (CO)5 ⟶
(CO)3 MnCF2 CF2 CF2 Mn(CO)5 + 2CO
Incidentally the F19 nmr spectrum of the binuclear derivative exhibits the expected
two resonances in a 2: 1 relative intensity ratio rather than an anomalous 1 : 1 : 1
pattern like the enigmatic hydrogen analog [Mn(CO),]z. The metal-carbon bond in
perfluoroalkylmetal carbonyl derivatives is much stronger than the metal carbon
bond in their hydrogen analogs.
This strengthening of the metal-carbon bond in perfluoroalkyl metal carbonyl

derivatives may be attributed to the contribution of "no-bond" resonance structures
such as the following for trifluoromethyl derivatives.
The concomitant weakening of the carbon-fluorine bonds in perfluoroalkylmetal

carbonyl derivatives is demonstrated by the following observations :
(a) lowering of the v(CF) infrared frequencies sometimes by as much as -150 cm-l
(as in the CF3 derivatives) relative to derivatives of the same fluorocarbon system
not bonded to a transition metal.
Page | 7
(b) relatively long carbon-fluorine distances found in X-ray crystallographic studies.
(c) relative ease of removal of fluorine by basic reagent.To date it has not been
possible to find preparative applications of the relative weakness of the carbon-
fluorine bond in perfluoroalkyl derivatives of transition metals.
The increased strength of the metal-carbon bond of perfluoroalkyl derivatives of

transition metals relative to nonfluorinated alkyl derivatives may be dramatic: e.g.,
CH3Co(CO)4 as mentioned decomposes above -35" while its fluorine analog,
CF&o(CO)4, is a liquid stable enough to survive distillation at atmospheric pressure
at about 90".
Catalytic activity of metal carbonyls:

Organometallic compounds in general and metal carbonyls in particular are known
to show catalytic activity.Most of the homogeneous catalytic cycles involve five
steps of reaction. Hence, it is imperative to understand these steps before studying
the catalytic cycles involved in different syntheses.
These steps are listed below:
➢ Coordination of ligand and its dissociation

➢ Migratory insertions and β-eliminations
➢ Nucleophilic attack on coordinated ligands
➢ Oxidations and reductions
➢ Oxidative additions and reductive eliminations
Page | 8
➢ Coordination of ligand and its dissociation
An efficient catalytic cycle requires a facile entry and exit of the ligand. Both
coordination and dissociation of ligand must occur with low activation free energy.
Labile metal complexes are therefore essential in catalytic cycles. Coordinatively
unsaturated complexes containing an open or weakly coordinated site are
labile.Square-planner 16-electron complexes are coordinatively unsaturated and are
usually employed to catalyse the reactions of organic molecules.
Catalytic systems involving ML4 complexes of Pd (II), Pt (II), and Rh (I), like
hydrogenation catalyst, [RhCl(PPh3)3] are well known.
➢ Migratory insertions and β-eliminations:
The migration of alkyl ligand to an unsaturated ligand is shown in the reaction below.
This reaction is an example of migratory insertion reaction.
The migration of hydride ligand to a coordinated alkene to produce a coordinated

alkyl ligand is shown in the reaction below.
Page | 9
Elimination is the reverse of insertion. Elimination of β- hydrogen is illustrated in

reaction shown below.
➢ Nucleophilic attack on coordinated ligands
The coordination of ligands like as carbon monoxide and alkenes to metal ions in
positive oxidation states activates the coordinated C atoms for a nucleophilic attack.
These reactions have found special attention in catalysis as well as organometallic
chemistry. The hydration of coordinated ethylene with Pd (II) is an example of
catalysis by nucleophilic activation. Stereochemical evidences indicate that the
reaction occurs by direct attack on the most highly substituted carbon atom of the
coordinated alkene:
Page | 10
➢ Oxidation and reduction:
The use of metal complexes in the catalytic oxidation of organic compounds is

popular. In these catalytic cycles, the metal atom shuttles between two oxidation
states. Examples of common catalytic one-electron couples are Cu2+/Cu+ ,
Co3+/Co2+, and Mn3+/Mn2+.
An example of catalytic two-electron couple is Pd2+/Pd. Catalysts containing metal

ions are also used in oxidation of hydrocarbons. The oxidation of xylene to
terephthalic acid is an example of such use. The metal ions play different roles in
these radical oxidation.
The metal atom shuttles back and forth between the two oxidation states in this pair
of reactions. A metal ion can also act as an initiator.
For example, when arenes are involved it is thought that the initiation occurs by a
simple redox process shown below: .
ArCH3 + Co(III) → ArCH3 + Co(II).
Page | 11
➢ Oxidative addition and reductive elimination
The oxidative addition of a molecule AX to a complex occurs by the dissociation of

the A−X bond followed by the coordination of two fragments as shown below:
The reductive elimination is reverse of the oxidative addition, and generally follows
it in a catalytic cycle. The mechanisms of oxidative addition reactions are different.
Depending upon reaction conditions and the nature of the reactants, there is evidence
for oxidative addition by simple concerted reaction, heterolytic (ionic) addition of
A+ and X- , or radical addition of A∙ and X∙. Even though, it has been observed that
the rates of oxidative addition of alkyl halides generally follow the orders Primary
alkyl < secondary alkyl < tertiary alkyl F << Cl < Br <I
Application of metal carbonyl cations to catalytic reactions:

Carbonylation of olefins and alcohols:
The Koch reaction has been well known for the synthesis of tertiary carboxylic acids
from olefins and water, or alcohols, with carbon monoxide in strong acids. The
reaction occurs at temperatures between 20 and 80 8C and pressures up to 100 atm.
Generally H2SO4, H3PO4, HF and BF3 H2O are employed as catalysts and solvents.
The Koch process was operated in commercial plants by Esso and Shell.
Page | 12
In concentrated H2SO4, for example, the olefin is protonated, or the alcohol is

protonated and dehydrated, to form a carbenium ion intermediate, which isomerizes
to tertiary carbenium ions via the Wagner/ Meerwein rearrangement prior to the
carbonylation.The carbonylation of the carbenium ions leads to the formation of
acylium cations, which react with water to give tertiary carboxylic acids or with
alcohols to give the corresponding esters.
However, olefins are converted to carboxylic acids in a yield lower than 10% under
atmospheric CO pressure owing to the presence of olefin oligomerization as a
competitive reaction. For achieving a high conversion to the corresponding
carboxylic acids, a high CO pressure is needed.
Haaf developed an alternative pressure-free variant with formic acid as the CO

source. However, this method has been restricted to the laboratory due to the high
cost of formic acid
H2 SO4
R − CH = CH2 + CO + H2 O R CR2 ⋅ COOH
high CO pressure − CH3
Very recently, the gold(I) carbonyl cations have been reported to work as an
excellent catalyst, with which olefins readily react with CO to produce tertiary
carboxylic acids in high yields at ambient pressure and temperature (Table 7) [65].
It is the first application of gold(I) carbonyls to organic syntheses, while very few
gold catalysts have been reported so far.
Page | 13
The influence of the H2SO4 concentration on the formation of Au(I) carbonyls and
on the carbonylation of 1-hexene. The dependence of the carbonylation on the H2SO4
concentration parallel to that of the formation of the unstable Au(I) dicarbonyl cation
Au(CO)2 leads to the conclusion that the gold dicarbonyl but not the monocarbonyl
is the active species for the carbonylation. Similar behavior was observed for the
Cu(I) catalyst, indicating that both Cu(CO)2 and Cu(CO)3 are the active species,
but Cu(CO) is inactive.
Applications Of Metal Carbonyl as Reagents and Catalysis

in Synthesis:
I. REDUCTION:(DESULFURIZATION, DEOXYGENATION)
Desulfurization reactions are of considerable current interest, particularly with
reference to applications for the removal of sulfur from fuel oil and flue gases.
Thiocarbonyl compounds can be converted to olefins and/or hydrocarbons by a
variety of metal carbonyls including dicobalt octacarbonyl, cyclopentadienyliron
dicarbonyl dimer , and molybdenum hexacarbonyl.
Page | 14
The latter Group VI metal carbonyl is a very useful reagent, not only for extracting
sulfur from thioketones, but from organic compounds containing carbon-sulfur
single bonds.
The metal carbonyl is active, either in acetic acid [where molybdenum(II) is

generated] or by adsorbance onto silica gel. Examples include the formation of
naphthalene from 2-naphthalenethiol, and the desulfurization of dibenzothiophene
to biphenyl.
Iron pentacarbonyl is a fine reagent for deoxygenating N-oxides, nitrones, nitrile

oxides, azoxy compounds, and sulfoxides . Deoxygenation and coupling occurs with
nitro compounds, while amines are efficiently produced by the use of triiron
dodecacarbonyl under phase transfer catalysis conditions.
Fe3 (CO)12
ArNO2
NaOH, C6 H6
PhCH2 N(C2 H5 )+ 3 Cl
−
r.t., 0.5 − 0.2hr.
Page | 15
The deoxygenation of epoxides by Fe(CO)5 in dipolar aprotic solvents such as

tetramethylurea (TMU) or N,N-dimethylacetamide is useful, both because good
yields of olefins can be attained and a variety of functionalities can be tolerated [e.g.,
sulfone, ester, ketone, alcohol, olefin]. Even alcohols can be deoxygenated by
Fe(CO)5. The latter process is effected by initial in situ generation of the alkoxide
ion, and then reacting it with the metal carbonyl.
Acid work-up affords the deoxygenated product, and destroys any metal carbonyl
residues. This deoxygenation procedure is applicable to alcohols capable of
generating reasonably stable carbanions .
Page | 16
Coupling Reactions:
➢ Halide Derivatives
Most of the work has been done on coupling reactions of halides mediated by metal
carbonyls. Of particular note is the chemistry of tetracarbonylferrate(II), which has
been reacted with saturated halides (or tosylate) to give ketones.
There is solid evidence for the intermediacy of acyltetracarbonylferrates in these

reactions.
Acyltetracarbonylferrates has been found to be exceedingly useful reagents for the

synthesis of l,3-oxazol-5-ones, an important class of mesoionic compounds.
This fascinating reaction occurs by exposure of imidoyl chlorides to the metal

carbonyl anion.
The location of substituent groups in the product suggests that a novel acyl migration
from iron to nitrogen is a key step in the reaction pathway.
Ligand migration of the carbon-iron i-bond to one of the terminal carbonyl carbons
may occur simultaneously or in a subsequent step.
An amido ketene, which is a known precursor to the l,3-oxazol-5-one, would result

from decomplexation.
Page | 17
What is particularly valuable about this reaction is that it provides an entry to simple
and polyfunctional ovamino acid derivatives, since the mesoionic compounds are
readily ring-opened by water or alcohol.
The reaction of imidoyl chlorides with acyltricarbonylnickelates appears to occur

via an electron-transfer pathway, affording cx-diketones and l,4-diaza-l,3-
butadienes as the principal products.
Page | 18
Uses of Metal carbonyls:

Metallurgical uses:
Metal carbonyls are used in several industrial processes. Perhaps the earliest
application was the extraction and purification of nickel via nickel tetracarbonyl by
the Mond process.
Carbonyl iron is used for the preparation of inductors, pigments, as dietary

supplements, in the production of radar-absorbing materials in the stealth
technology, and in thermal spraying.
Catalysis:
Metal carbonyls are used in a number of industrially important carbonylation

reactions.In the oxo process, an olefin, dihydrogen, and carbon monoxide react
together with a catalyst (e.g. dicobalt octacarbonyl) to give aldehydes. Illustrative is
the production of butyraldehyde;
H2 + CO + CH3CH=CH2 → CH3CH2CH2CHO
Butyr aldehyde is converted on an industrial scale to 2-ethylhexanol, a precursor to

PVC plasticizers, by aldol condensation, followed by hydrogenation of the resulting
hydroxyaldehyde. The "oxo aldehydes" resulting from hydroformylation are used
for large-scale synthesis of fatty alcohols.
Page | 19
Hydroformulation mechanism:
Another important reaction catalyzed by metal carbonyls is the hydrocarboxylation.
➢ Hydrocarboxylation of acetylene with an alcohol:
Also the cyclization of acetylene to cyclooctatetraene uses metal carbonyl

catalysts;In the Monsanto and Cativa processes, acetic acid is produced from
methanol, carbon monoxide, and water using hydrogen iodide as well as rhodium
and iridium carbonyl catalysts, respectively. Related carbonylation reactions afford
acetic anhydride.
➢ CO-releasing molecules (CO-RMs):
Carbon monoxide-releasing molecules are metal carbonyl complexes that are being
developed as potential drugs to release CO. At low concentrations, CO functions as
a vasodilatory and an anti-inflammatory agent. CO-RMs have been conceived as a
pharmacological strategic approach to carry and deliver controlled amounts of CO
to tissues and organs.
Page | 20
References:
▪ H. Alper (ed.), Transition Metal Organometallics in Organic Synthesis,
Academic Press, New York, Volume I, 1976; Volume II, 1978.
▪ 2. H. Alper and H.N. Paik, J. Org. Chem., 42, 3522 (1977)

▪ https://nptel.ac.in/content/storage2/courses/104106064/lectures.pdf
▪ Visited on 4/1/2022 at 11:18 am
▪ https://nptel.ac.in/content/storage2/courses/104106064/lectures.pdf
▪ Visited on 4/2/2022 at 2:35 pm
▪ https://www.degruyter.com/document/doi/10.1351/pac198052030607/html
Visited on 5/1/2022 at 10:02 am
▪ Sci-Hub | Metal carbonyl cations: generation, characterization and catalytic
application | 10.1016/s0010-8545(02)00115-7 (hkvisa.net) Visited on
6/1/2022 at 4:22pm
Page | 21

Metal Carbonyls

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Metal Carbonyls

Uploaded by

Copyright:

Available Formats

Assignment#1

Applications of Metal Carbonyls & their derivatives

Submitted by : Alsha Mehwish

Msc Chemistry III

Course title: Inorganic chemistry-V

Course Code: CHEM-402 (Fall 2021)

Submitted by: ALSHA MEHWISH

Class: Msc Chemistry-III

Submission date: Jan 10,2022

APPLICATIONS OF METAL CARBONYL’S DERIVATIVES……………………………. 3

Ni(CO)4, Nickel tetracarbonyl………………………………………………………………………………………. 4

Cr(CO)6, Chromium hexacarbonyl…………………………………………………………………………………. 4

Fe3(CO)12, Triiron dodecacarbonyl…………………………………………………………………………………. 5

FLUOROCARBON DERIVATIVES OF METAL CARBONYLS…………………………. 6

CATALYTIC ACTIVITY OF METAL CARBONYLS……………………………………… 8

APPLICATION OF METAL CARBONYL CATIONS TO CATALYTIC REACTIONS.12

APPLICATIONS OF METAL CARBONYL AS REAGENTS IN SYNTHESIS…………. 14

USES OF METAL CARBONYLS……………………………………………………………. 19

Applications Of Metal carbonyl’s derivatives:

Ni(CO)4, Nickel tetracarbonyl:

➢ It is used for plating nickel on other metals.

Cr(CO)6, Chromium hexacarbonyl:

➢ It reacts with sodium metal in liquid ammonia to give carbonylate anion.

➢ It gives substitution reactions with amines like en and py. At higher

Cr(CO)6 + 2py → Cr(CO)4 (py)2 + 2C

Fe3(CO)12, Triiron dodecacarbonyl:

It gives substitution reaction with pyridine and methanol.

3Fe3 (CO)12 + 3py → Fe3 (CO)9 (py)3 + 3Fe(CO)5

It reacts with sodium metal in ammonia to give carbonylate anion.

It reacts with nitric oxide to form iron dicarbonyl dinitrosyl.

Fluorocarbon Derivatives of Metal Carbonyls:

NaMn(CO)3 + C2 F3 I ⟶ THFu (CO)E I + NaF + CF2 = CF2

The difference in the behavior of perfluoroalkyl iodides and that of nonfluorinated

A two-step procedure involving decarbonylation of the corresponding

2N2 Mn(OO)2 + ClCOCF2 CF2 CF3 COCl THF

This strengthening of the metal-carbon bond in perfluoroalkyl metal carbonyl

The concomitant weakening of the carbon-fluorine bonds in perfluoroalkylmetal

(b) relatively long carbon-fluorine distances found in X-ray crystallographic studies.

The increased strength of the metal-carbon bond of perfluoroalkyl derivatives of

Catalytic activity of metal carbonyls:

These steps are listed below:

➢ Coordination of ligand and its dissociation

➢ Coordination of ligand and its dissociation

➢ Migratory insertions and β-eliminations:

The migration of hydride ligand to a coordinated alkene to produce a coordinated

Elimination is the reverse of insertion. Elimination of β- hydrogen is illustrated in

➢ Nucleophilic attack on coordinated ligands

➢ Oxidation and reduction:

The use of metal complexes in the catalytic oxidation of organic compounds is

An example of catalytic two-electron couple is Pd2+/Pd. Catalysts containing metal

ArCH3 + Co(III) → ArCH3 + Co(II).

➢ Oxidative addition and reductive elimination

The oxidative addition of a molecule AX to a complex occurs by the dissociation of

Application of metal carbonyl cations to catalytic reactions:

In concentrated H2SO4, for example, the olefin is protonated, or the alcohol is

Haaf developed an alternative pressure-free variant with formic acid as the CO

Applications Of Metal Carbonyl as Reagents and Catalysis

The metal carbonyl is active, either in acetic acid [where molybdenum(II) is

Iron pentacarbonyl is a fine reagent for deoxygenating N-oxides, nitrones, nitrile

r.t., 0.5 − 0.2hr.

The deoxygenation of epoxides by Fe(CO)5 in dipolar aprotic solvents such as

There is solid evidence for the intermediacy of acyltetracarbonylferrates in these

Acyltetracarbonylferrates has been found to be exceedingly useful reagents for the