Inorganic Chemistry (CHEM - 363) [Link]@[Link].

pk

Metal Carbonyls & Its Derivatives

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.

Historical Background

Initial experiments on the reaction of carbon monoxide with metals

were carried out by "Justus von Liebig" in 1834. By passing carbon
monoxide over molten potassium he prepared a substance having the
empirical formula KCO, which he called "Kohlenoxidkalium".

The synthesis of the first true heteroleptic metal carbonyl complex

was performed by "Paul Schützenberger" in 1868 by passing chlorine and
carbon monoxide over platinum black, where dicarbonyldichloroplatinum
(Pt(CO)2Cl2) was formed.

One of the founders of Imperial Chemical Industries,"Ludwig Mond",

investigated in the 1890s with "Carl Langer" and "Friedrich Quincke"
various processes for the recovery of chlorine. They found that the
resulting gas colored the gas flame of a burner in a greenish-yellowish
color; when heated in a glass tube it formed a nickel mirror. The gas could
be condensed to a colorless, water-clear liquid with a boiling point of 43 °C.
Thus, Mond and his coworker had discovered the first pure, homoleptic
metal carbonyl, nickel tetracarbonyl (Ni(CO)4).

"Mond" and "Marcellin Berthelot" independently discovered iron

pentacarbonyl,the following year. "James Dewar" and "H. O. Jones" were
able to determine the structure of di-iron nonacarbonyl, In 1906, which is
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produced from iron pentacarbonyl by the action of sunlight. After Mond,

who died in 1909, the chemistry of metal carbonyls fell for several years in
oblivion. The iron pentacarbonyl was used for the production of high-purity
iron, so-called carbonyl iron, and iron oxide pigment.

In 1928, "Walter Hieber" played decisive role in the development of

metal carbonyl chemistry. He systematically investigated and discovered,
among other things, the "Hieber" base reaction, the first known route to
metal carbonyl hydrides and synthetic pathways leading to metal carbonyls
such as dirhenium decacarbonyl. "Hieber", who was the Director of the
Institute of Inorganic Chemistry at the Technical University since 1934
"Munich" published in four decades 249 papers on metal carbonyl
chemistry.

"Walter Reppe", An industrial chemist and later board member of the

BASF, in 1930 discovered a number of homogeneous catalytic processes,
such as the hydrocarboxylation, in which olefins or alkynes react with
carbon monoxide and water to form products such as unsaturated acids
and their derivatives.

New complexes of the concept of the isolobal analogy has been

found useful for the rational design. In chemistry for the development of
the concept "Roald Hoffmann" was awarded with the noble prize. The
concept describes metal carbonyl fragments of M(CO)n as parts of
octahedral building blocks in analogy to the tetrahedral CH3-, CH2- or CH-
fragments in organic chemistry. In his Nobel Prize lecture Hoffmann
emphasized that the isolobal analogy is a useful but simple model, and in
some cases does not lead to success.

Introduction:

Nomenclature and terminology:

The metal carbonyl nomenclature depends on the charge of the

complex, the number and type of central atoms, the number and type of
ligands and their binding modes. They occur as neutral complexes, as
positively charged metal carbonyl cations or as negatively charged metal
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carbonyl anion. The carbon monoxide ligand may be bound terminally to a

single metal atom or bridging to two or more metal atoms. These
complexes may be homoleptic, that is containing only CO ligands, such as
nickel tetracarbonyl (Ni(CO)4), but more commonly metal carbonyls are
heteroleptic and contain a mixture of ligands. Complexes with different
metals, but only one type of ligand are called isoleptic.

Occurrence in nature:

Iron carbonyl clusters were also observed in Jiange H5 chondrites

identified by infrared spectroscopy. Four infrared stretching frequencies
were found for the terminal and bridging carbon monoxide [Link] the
oxygen-rich atmosphere of earth metal carbonyls are subject to oxidation to
the metal oxides.

Traces of the carbonyls of iron, nickel, and tungsten were found in the
gaseous emanations from the sewage sludge of municipal treatment
[Link] hydrogenase enzymes contain CO bound to iron. Apparently the
CO stabilizes low oxidation states, which facilitates the binding of hydrogen.
Carbon monoxide containing complexes are invoked for the toxicity of CO
and signalling.

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CLASSIFICATION OF METAL CARBONYLS:

Different types of metal carbonyls with examples are given below;

Types. Examples
Mononuclear carbonyls [Ti(CO)6]-2, [V(CO)6], [Cr(CO)6] ,[Fe(CO)5],
[Ni(CO)4]
Dinuclear carbonyls [Mn2(CO)10], [Fe2(CO)9], [Co2(CO)8]
Polynuclear carbonyls [Fe3(CO)12], [Co4(CO)12], [Co6(CO)16]
µ2-Bridging carbonyls [Fe2(CO)9], [Co2(CO)8], [Fe3(CO)12], [Co4(CO)12]
µ3-Bridging carbonyls [Rh6(CO)16] (Four triply bridged carbonyl
groups)

Carbonyl hydrides [HMn(CO)5], [HCo(CO)4], [H2Fe(CO)4]

Mononuclear (monomeric) carbonyls:

These compounds which contain only one metallic atom per molecule.

Ni(CO)4, Nickel tetracarbonyl:

Preparation:
It can be prepared by passing carbon monoxide over nickel in the
temperature range of 60-100oC.

Ni + 4CO→Ni(CO)4 At 600C
It can also be prepared by passing carbon monoxide through alkaline
suspensions of nickel sulphide or nickel cyanate.

NiS + 4CO→ Ni(CO)4 + S

Ni(CN)2 + 4 CO→ Ni(CO)4 + C2N2

Properties:

It is a colourless liquid having melting point -25oC, boiling point 43oC

and decomposition temperature in the range of 180 [Link] is insoluble in
water but dissolves in organic solvents.
It reacts with concentrated sulphuric acid along with detonation. It reacts
with moist nitric oxide to give deep blue coloured compound.
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Uses:

Since Ni(CO)4, on heating, decomposes to metallic nickel, it is used in the

production of nickel by mond's [Link] is used for plating nickel on other
[Link] is used as a catalyst for synthesis of acrylic monomers in plastic
industries.

Structure:

Fe(CO)5, Iron pentacarbonyl:

Preparation:
It can be prepared by passing carbon monoxide over iron powder at high
temperature and pressure.
Fe + 5CO→Fe(CO)5. At. 2000C, 100 atm
It can also be prepared by carbonylation of ferrous sulphide/iodide in
presence of Cu-metal, which acts as a reducing agent.
2FeS + 10CO + 2Cu→Fe(CO)5 + Cu2S At. 2000C, 200 atm
Properties:
It is a pale yellow liquid having melting point -20oC, boiling point 103oC and
decomposition temperature around 250oC. It is insoluble in water but
soluble in glacial acetic acid, methanol, diethyl ether, acetone and benzene.
Cold solution of iron pentacarbonyl in glacial acetic acid undergoes
dimerization under the influence of ultra-violet light. It is readily hydrolysed
by water and acids.

Fe(CO)5 + H2SO4 → FeSO4 + 5CO + H2

Structure:
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Cr(CO)6, Chromium hexacarbonyl:

Preparation:
It can be prepared by carbonylation of chromium chloride with carbon
monoxide using a reducing agent like lithium aluminium hydride (LAH).
CrCl3 + 6CO→ Cr(CO)6 At. LAH, 1150C, 70 atm
Properties:
It is a white crystalline solid melting above 150oC and boiling at 220oC. It is
insoluble in water but soluble in ether, chloroform, carbon tetrachloride and
benzene. It is not attacked by air, bromine, cold aqueous alkalis, dilute
acids and concentrated hydrochloric acid as well as sulphuric acid. It is
decomposed by Chlorine gas and concentrated nitric acid. It reacts with
fluorine at -75oC to form chromium hexafluoride.
Structure:

POLYNUCLEAR CARBONYLS:
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These contain two or more metallic atoms per molecule and are of the type
Mx(CO)y. These carbonyls are also sometimes called as bridged carbonyls.
Polynuclear carbonyls may be homonuclear.
Mn2(CO)10, Dimanganese decacarbonyl:
Preparation:
It can be prepared by carbonylation of manganese iodide with carbon
monoxide using magnesium as a reducing agent.
2MnI2 +10CO + 2Mg → Mn2 (CO)10 + 2MgI2. At. 250 C, 210 atm
Properties:
It forms stable golden yellow crystals having melting point of 155oC. It is
oxidized by trace amount of oxygen in solution. Hence, the solution must
be stored in inert atmosphere.
Structure:

Co2(CO)8, Dicobalt octacarbonyl:

Preparation:
It can be prepared by direct combination of carbon monoxide with cobalt
metal.
2Co + 8CO →Co2 (CO)8 At. 200°C, 100 atm
Properties:

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It is an orange crystalline substance having melting point 51oC and turns

deep violet upon exposure to air. It is soluble in alcohols, ether and carbon
tetrachloride. Upon heating at 50oC it forms tetracobalt dodecacarbonyl.
2Co2 (CO)8 →Co4 (CO)12 + 4CO At. 50°C
Structure:

Fe2 (CO) 9, Diiron nonacarbonyl:

Preparation:
Cold solution of iron pentacarbonyl in glacial acetic acid undergoes
dimerization under the influence of ultra-violet light to give golden yellow
crystals.
2Fe(CO)5 → Fe2(CO)9 + CO At. hv
Properties:
Diiron nonacarbonyl forms golden yellow triclinic crystals melting at 100oC.
It is insoluble in water but soluble in toluene and pyridine.
Structure:

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Fe3(CO)12, Triiron dodecacarbonyl:

Preparation:
It is prepared by heating diiron nonacarbonyl dissolved in toluene at 70oC.
3Fe2(CO)9 → 3Fe(CO)5 + (CO)12 At. 70°C, Toluene
Properties:
It forms green monoclinic crystals which are soluble in organic solvents like
toluene, alcohol etc.
It decomposes at 140oC to give metallic iron and carbon monoxide.
Fe3(CO)12→3Fe +12CO At. 140°C
Structure:

SYNTHESIS OF METAL CARBONYLS:

The general methods of preparation of metal carbonyls are given below;

Since the work of Mond and Hieber, many procedures have been
developed for the preparation of mononuclear metal carbonyls as well as
homo-and hetero-metallic carbonyl clusters.

Direct reaction of metal with carbon monoxid:

Nickel tetracarbonyl and iron pentacarbonyl can be prepared according to

the following equations by reaction of finely divided metal with carbon
monoxide.

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Ni + 4 CO → Ni(CO)4 (1 bar, 55°C)

Fe + 5 CO → Fe(CO)5 (100 bar, 175°C)

Reduction of metal salts and oxides:

Some metal carbonyls are prepared by the reduction of metal halides in the
presence of high pressure of carbon monoxide. A variety of reducing
agents are employed, including copper, aluminum, hydrogen, as well as
metal alkyls such as triethylaluminium. Illustrative is the formation of
chromium hexacarbonyl from anhydrous chromium(III) chloride in benzene
with aluminum as a reducing agent, and aluminum chloride as the catalyst.

CrCl3 + Al + 6 CO → Cr(CO)6 + AlCl3

Photolysis and thermolysis:

Photolysis or thermolysis of mononuclear carbonyls generates bi- and

multimetallic carbonyls such as diiron nonacarbonyl (Fe2(CO)9). On further
heating, the products decompose eventually into the metal and carbon
monoxide.

2 Fe(CO)5 → Fe2(CO)9 + CO

Salt metathesis:

Salt metathesis reaction of for example KCo(CO)4 with [Ru(CO)3Cl2]2 leads

selectively to mixed-metal carbonyls such as RuCo2(CO)11.

4 KCo(CO)4 + [Ru(CO)3Cl2]2 → 2 RuCo2(CO)11 + 4 KCl + 11 CO

Metal carbonyl cations and carbonylates:

The synthesis of ionic carbonyl complexes is possible by oxidation or

reduction of the neutral complexes. Anionic metal carbonylates can be
obtained for example by reduction of dinuclear complexes with sodium.

Example is the sodium salt of iron tetracarbonylate (Na2Fe(CO)4, Collman's

reagent), which is used in organic [Link] cationic hexacarbonyl
salts of manganese, technetium and rhenium can be prepared from the

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carbonyl halides under carbon monoxide pressure by reaction with a Lewis

acid.

Mn(CO)5Cl + AlCl3 + CO → Mn(CO)6+ + AlCl4−

The use of strong acids succeeded in preparing gold carbonyl cations such
as [Au(CO)2]+, which is used as a catalyst for the carbonylation of olefins.

Reaction:

Metal carbonyls are important precursors for the synthesis of other

organometalic complexes. The main reactions are the substitution of
carbon monoxide by other ligands, the oxidation or reduction reactions of
the metal center and reactions of carbon monoxide ligand.

CO substitution:

The substitution of CO ligands can be induced thermally or photochemically

by donor ligands. The range of ligands is large, and includes phosphines,
cyanide (CN−), nitrogen donors, and even ethers, especially chelating one.
Olefins, especially diolefins, are effective ligands that afford synthetically
useful derivatives. Substitution of 18-electron complexes generally follows
a dissociative mechanism, involving 16-electron intermediates.

Substitution proceeds via a dissociative mechanism:

M(CO)n → M(CO)n-1 + CO

M(CO) n-1 + L → M(CO)n-1L

The dissociation energy is 105 kJ mol−1 for nickel tetracarbonyl and 155 kJ
mol−1 for chromium hexacarbonyl. Substitution in 17-electron complexes,
which are rare, proceeds via associative mechanisms with a 19-electron
intermediates.

M(CO)n + L → M(CO)nL

M(CO)nL → M(CO)n-1L + CO

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The rate of substitution in 18-electron complexes is sometimes catalysed

by catalytic amounts of oxidants, via electron-transfer.

Reduction:

Metal carbonyls react with reducing agents such as metallic sodium or

sodium amalgam to give carbonylmetalate (or carbonylate) anions.

Mn2(CO)10 + 2 Na → 2 Na[Mn(CO)5]

For iron pentacarbonyl, one obtains the tetracarbonylferrate with loss of CO.

Fe(CO)5 + 2 Na → Na2[Fe(CO)4] + CO

Mercury can insert into the metal-metal bonds of some polynuclear metal
carbonyls.

Co2(CO)8 + Hg → (CO)4Co-Hg-Co(CO)4

Nucleophilic attack at CO:

The CO ligand is often susceptible to attack by nucleophiles. For example,

trimethylamine oxide and bistrimethylsilylamide convert CO ligands to CO2
and CN−, respectively. In the "Hieber base reaction", hydroxide ion attacks
the CO ligand to give a metallacarboxylic acid, followed by the release of
carbon dioxide and the formation of metal hydrides or carbonylmetalates. A
good example of this nucleophilic addition reaction is the conversion of iron
pentacarbonyl to hydridoiron tetracarbonyl anion:

Fe(CO)5 + NaOH → Na[Fe(CO)4CO2H]

Na[Fe(CO)4COOH] + NaOH → Na[HFe(CO)4] + NaHCO3

Protonation of the hydrido anion gives the neutral iron tetracarbonyl hydride.

Na[HFe(CO)4] + H+ → H2Fe(CO)4 + Na+

With electrophile:

Despite being in low formal oxidation states, metal carbonyls are relatively
unreactive toward many electrophiles. For example, they resist attack by

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alkylating agents, mild acids, mild oxidizing agents. Most metal carbonyls
do undergo halogenation. Iron pentacarbonyl, for example, forms ferrous
carbonyl halides:

Fe(CO)5 + X2 → Fe(CO)4X2 + CO

Metal-metal bonds are cleaved by halogens. Depending on the electron-

counting scheme used, this can be regarded as oxidation of the metal atom:

Mn2(CO)10 + Cl2 → 2 Mn(CO)5Cl

Structure and bonding:

Carbon monoxide bonds to transition metals using "synergistic π* back-

[Link] rise to a partial triple bond the bonding has three
components. The latter kind of binding requires that the metal have d-
electrons, and that the metal is in a relatively low oxidation state (<+2)
which makes the back donation process favorable. As electrons from the
metal fill the π-antibonding orbital of CO, they weaken the carbon-oxygen
bond compared with free carbon monoxide, while the metal-carbon bond is
strengthened.

Infrared spectroscopy is a sensitive probe for the presence of bridging

carbonyl ligands. For compounds with doubly bridging CO ligands, denoted
μ2-CO or often just μ-CO, νCO, νCO is usually shifted by 100–200 cm−1 to
lower energy compared to the signatures of terminal CO, i.e. in the region
1800 cm−1. Bands for face capping (μ3) CO ligands appear at even lower
energies. In addition to symmetrical bridging modes, CO can be found
bridge unsymmetrically or through donation from a metal d orbital to the π*
orbital of CO. The increased π-bonding due to back-donation from multiple
metal centers results in further weakening of the C-O bond.

Compound:

Most metal carbonyl complexes contain a mixture of ligands. Examples

include the historically important IrCl(CO)(P(C6H5)3)2 and the anti-knock
agent (CH3C5H4)Mn(CO)3. The formula of many metal carbonyls can be
inferred from the 18 electron rule.
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PHYSICAL PROPERTIES:
State:

Majority of the metallic carbonyls are liquids or volatile solids.

Colour:

Most of the mononuclear carbonyls are colourless to pale yellow.

Polynuclear carbonyls exhibit are dark in colour.

Solubility:

Metal carbonyls are soluble in organic solvents like glacial acetic acid,
acetone, benzene, carbon tetrachloride and ether.

Toxicity:

Nickel tetracarbonyl exhibits strongest inhalation toxicity. These

compounds are carcinogenic over long-term [Link] to low melting
points and poor thermal stability, they show toxicity related to the
corresponding metal and carbon monoxide. Exposure to these compounds
can cause damage to lungs, liver, brain and kidneys.

Magnetic Property:

All the metal carbonyls other than vanadium hexacarbonyl are

[Link] case of dinuclear metal carbonyls formed by metals with
odd atomic number, the unpaired electrons are utilized for the formation of
metal-metal bonds.

Thermal Stability:

Most of the metal carbonyls melt or decompose at low temperatures. Solid

carbonyls sublime in vacuum but they undergo some degree of
[Link] Stability:Metal carbonyls are
thermodynamically unstable. They undergo aerial oxidation with different
rates. Co2(CO)8 and Fe2(CO)9 are oxidized by air at room temperature while
chromium and molybdenum hexacarbonyls are oxidized in air when heated.

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CHEMICAL PROPERTIES:
The metal carbonyls give a variety of chemical reactions.
Ligand substitution reactions:
Substitution of carbon monoxide ligand by various mono dentate and
bidentate ligands can be carried out using thermal and photochemical
reactions. Monodentate ligands like isocyanides(CNR), cyanide (CN-),
phosphine (PR3) and ethers can partially or completely replace the
carbonyl group.

Fe (CO)5 + 2CNR→ Fe(CO)3(CNR)2 + 2CO

Ni(CO)4 + 4CNR→ Ni(CNR)4 + 4CO

Reaction with metallic sodium:

Metallic sodium and its amalgam can be used to reduce the metal
carbonyls.

Cr(CO)6 + 2 Na → Na2 [Cr(CO)5] + CO

Mn2 (CO)10 + 2 Na → 2 Na[Mn(CO)5] + CO
In the above two reactions, the Cr and Mn atoms in their zero oxidation
states are reduced to -2 and -1 oxidation states respectively.
Reaction with sodium hydroxide:
The reaction of sodium hydroxide with metal carbonyls results in
nucleophilic attack by hydroxide ion on the carbonyl group to give a metal
carboxylic acid complex. Upon further action with sodium hydroxide, the
carboxylic acid gives up carbon dioxide to form a hydrido anion. The
protonation of this anion results in the formation of iron tetracarbonyl
hydride as shown below:

Fe(CO)5 + NaOH→ Na[Fe(CO)4COOH]

Na[Fe(CO)4COOH] + NaOH → Na[HFe(CO)4] + NaHCO3
Na[HFe(CO)4] + H+ → (H)2 Fe(CO)4 + Na+
The above reaction is known as Heiber base reaction.

Reaction with halogens:

Most of the metal carbonyls react with halogens to give carbonyl halides.

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Fe(CO)5 + X2 → Fe(CO)4 X2 + CO
Mo(CO)6 + Cl2 → Mo(CO)4 Cl2 + 2CO
Reaction with hydrogen:
Some of the carbonyls can be reduced by hydrogen to give carbonyl
hydrides

Co2(CO)8+ H2 → 2[Co(CO)4H] At. 1650C, 200 atm

Mn2(CO)10 + H2 → 2[Mn(CO)5H] At. 200 atm
Reaction with nitric oxide:
A good number of metal carbonyls react with nitric oxide to give carbonyl
nitrosyls.

Fe(CO)5 + 2NO → Fe(CO)2(NO)2 + 3CO At. 950C

Co2(CO)8 + 2NO → 2Co(CO)3(NO) + 2CO At. 400C

The reaction between iron pentacarbonyl and nitric oxide involves
replacement of three carbonyl groups by two nitric oxide molecules.
Electronically, this is equivalent as nitric oxide is a three electron donor
ligand whereas carbon monoxide is a two electron donor.

Analytical characterization:

Apart from X-ray crystallography, important analytical techniques for the

characterization of metal carbonyls are infrared spectroscopy and 13C-
NMR spectroscopy. Infrared active vibrational modes, such as CO-
stretching vibrations are often fast compared to intramolecular processes,
whereas NMR transitions occur at lower frequencies and thus sample
structures on a time scale that, it turns out, is comparable to the rate of
intramolecular ligand exchange processes.

Iron pentacarbonyl Iron pentacarbonyl exhibits only a single 13C-NMR

signal owing to rapid exchange of the axial and equatorial CO ligands by
Berry pseudorotation.

Infrared spectra:

An important technique for characterizing metal carbonyls is infrared

spectroscopy. The C-O vibration, typically denoted νCO, occurs at 2143
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cm−1 for CO gas. The energies of the νCO band for the metal carbonyls
correlates with the strength of the carbon-oxygen bond, and inversely
correlated with the strength of the π-backbonding between the metal and
the carbon.

The number of observable IR transitions (but not the energies) can thus be
predicted. For example, the CO ligands of octahedral complexes, e.g.
Cr(CO)6, transform as a1g, eg, and t1u, but only the t1u mode (anti-
symmetric stretch of the apical carbonyl ligands) is IR-allowed. Spectra for
complexes of lower symmetry are more complex. For example, the IR
spectrum of Fe2(CO)9 displays CO bands at 2082, 2019, 1829 cm−1. The
number of IR-observable vibrational modes for some metal carbonyls.

Nuclear magnetic resonance spectroscopy:

Metal carbonyls are often characterized by 13C NMR spectroscopy. To

improve the sensitivity of this technique, complexes are often enriched
13CO. Typical chemical shift range for terminally bound ligands is 150 to
220 ppm. Bridging ligands resonate between 230 and 280 ppm. The 13C
signals shift toward higher fields with an increasing atomic number of the
central metal.

The activation energy of ligand exchanges processes can be determined

by the temperature dependence of the line broadening.

Mass spectrometry:

Mass spectrometry provides information about the structure and

composition of the complexes. Spectra for metal polycarbonyls are often
easily interpretable, because the dominant fragmentation process is the
loss of carbonyl ligands (m/z= 28).

M(CO)n+ → M(CO)n-1 + CO

Electron ionization is the most common technique for characterizing the

neutral metal carbonyls. Neutral metal carbonyls can be converted to
charged species by derivatization, which enables the use of electrospray
ionization, instrumentation for which is often widely available. For example,
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treatment of a metal carbonyl with alkoxide generates an anionic

metallaformate that is amenable to analysis by ESI-MS;

LnM(CO) + RO_ → [LnM-C(=O)OR]_

Some metal carbonyls react with azide to give isocyanato complexes with
release of nitrogen. By adjusting the cone voltage and/or temperature, the
degree of fragmentation can be controlled. The molar mass of the parent
complex can be determined, as well as information about structural
rearrangements involving loss of carbonyl ligands under ESI-MS conditions.

Mass spectrometry combined with infrared photodissociation spectroscopy

can provide vibrational informations for ionic carbonyl complexes in gas
phase.

Applications:

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 (see also carbonyl metallurgy).

Carbonyl iron is used inter alia 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

Butyraldehyde 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"

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resulting from hydroformylation are used for large-scale synthesis of fatty

alcohols.

Hydroformulation mechanism:

Another important reaction catalyzed by metal carbonyls is the

hydrocarboxylation. The example below is for the synthesis of acrylic acid
and acrylic acid esters.

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.

Application
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.

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