CHAPTER 11 Metal-Π Complexes: 439

 Vibrational Spectra of Metal Carbonyls for Bonding and Structure

Elucidation
Vibrational spectroscopy is one of the most important methods used for the characterization of metal
carbonyls. This technique provides very useful information not only about the structural prototype of different
metal carbonyl compositions but also rationalizes the nature of bonding in them. Now, it is quite a well-known
fact that the C–O vibration for free carbonyl group (CO gas) is typically denoted as ν CO, and absorbs at 2143
cm−1. However, this C–O absorption shifts downward (sometimes upward) to cover a very wide range of
wavenumber as the carbonyl ligand gets attached to a metal center. This is obviously due to the fact that the
energies of the νCO band for the metal carbonyls directly correlate with the strength of the carbon-oxygen bond,
and are inversely correlated with the strength of the π-backbonding between the metal and the carbon. In other
words, the molecular orbital diagram of carbonyl group suggests that the highest occupied molecular orbital,
used for σ-donation is weakly bonding; but the lowest unoccupied molecular orbital, used for accepting d-
electron density from metal center is strongly antibonding; therefore, the σ-donation does not affect the CO
bond order very much but the acceptance of electron density in π * orbital decreases the bond order and
consequently the bond strength in a significant way. This effect reduces the force constant of C–O bond, while
the magnitude of force constant for M–C will be increased by this backbonding. As a result, the enhancement
of backbonding shifts the metal-carbon and carbon-oxygen stretching to higher and lower values, respectively.
The main features about the bonding and structure of metal carbonyls which can be obtained from the
vibrational spectra of metal carbonyls are discussed below:
 1. π-Basicity of the Metal Centre
The π-basicity of the metal center (and thus the C–O stretching frequency) depends upon a lot of
factors like the nature and magnitude of the charge on metal center, and the π-accepting tendency of ligands
attached other than the carbonyl. A negative charge on the metal center, or ligands with greater σ-donation and
weaker π-accepter strength, are expected to decrease the CO stretching frequency; while an accumulation of
positive charge on metal center, or ligands with weaker σ-donation stronger π-accepter strength are bound to
increase the CO stretching frequency. For example, in the isoelectronic series of Ti⟶Fe, the hexacarbonyls
show decreasing π-backbonding as one increases (makes more positive) the charge on the metal.

Compound [Ti(CO)6]2− [V(CO)6]1− [Cr(CO)6] [Mn(CO)6]1+ [Fe(CO)6]2+

νCO (cm−1) 1748 1859 2000 2095 2204

Compound [Hf(CO)6]2− [Ta(CO)6]1− [W(CO)6] [Re(CO)6]1+ [Os(CO)6]2+

νCO (cm−1) 1757 1850 1977 2085 2190

Hence, π-basic ligands increase π-electron density at the metal, and improved backbonding reduces νCO.

Copyright © Mandeep Dalal

 440 A Textbook of Inorganic Chemistry – Volume I

 2. Toleman Electronic Parameter

The electron-donating or withdrawing ability of a ligand is calculated in terms of the Tolman
electronic parameter (TEP), named after the inventor, Chadwick A. Tolman. It is determined by measuring the
frequency of the A1 vibrational mode of the carbonyl group in complex, Ni(CO)3L by infrared spectroscopy,
where L is the ligand being studied. Ni(CO)3L was chosen as the model compound because such complexes
can easily be synthesized from Ni(CO)4.

The CO band is pretty much unique and is rarely affected by other bands in the analyte's IR spectra. Moreover,
owing to the small size of carbonyl ligand, steric factors do not muddle the analysis. The coordination of CO
to a metal typically decreases νCO value from 2143 cm−1 (free CO). This can be rationalized by π-backbonding,
resulting from the sidewise overlap of metal orbitals of π-symmetry with the empty anti-bonding π* orbitals
on CO ligand. This increases the strength of the metal-carbon bond, but also weakens the C−O bond. If some
other ligand enhances the π-electrons-density on the metal, the CO bond strength decreases and so the νCO
value. On the other hand, if other ligands present compete with CO for π-backbonding, νCO increases. TEPs
for selected phosphines are given below.

L P(t-bu)3 P(Me)3 P(Ph)3 P(OEt)3 PCl3 PF3

νCO (cm−1) 2056.1 2064.1 2068.9 2076.3 2097.0 2110.8

The Tolman electronic parameter has been widely used to characterize the electronic properties of phosphine
based ligands.
 3. Structural Prototype of Metal Carbonyls
The symmetry behavior of different metal carbonyls can be used to determine the number of infrared
active vibrational modes, which in turn enable us to comment on structural prototypes. In other words, it is
well known from the group theory that only those vibrational modes will be observed which transform as the
electric-dipole moment operator; therefore, the number of observable infrared transitions for a particular
geometry can be predicted theoretically. These predictions are then matched with the experimentally observed
infrared spectra to shortlist the various possible structural prototypes. For instance, consider the case of five-
coordinated homoleptic metal carbonyl complexes. The two possible geometries are square-pyramidal and
trigonal bipyramidal.

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Square pyramidal
Trigonal bipyramidal

Figure 13. Two possible geometries of Iron pentacarbonyl i.e. Fe(CO)5 complex.

For trigonal bipyramidal geometry, a reducible representation based on five C–O bonds is:

D3h E 2C3 3C2 σh 2S3 3σd Irreducible components

Γπ 5 2 1 3 0 3 2A1´ + A2´´ + E´

Out of four irreducible representations, A2´´ transforms as z-component while E´ transforms with x- and y-
components of the dipole moment. Now, owing to two doubly degenerate vibrational modes (E´), only two
peaks are expected in the experimental infrared spectrum. However, in the Raman infrared spectrum, three
peaks are expected as only 2A1´ and E´ irreducible components transform alongside the polarizability tensors.
For square pyramidal geometry, a reducible representation based on five C–O bonds is:

C4v E 2C4 C2 2σv 2σd Irreducible components

Γπ 5 2 1 3 3 2A1 + B1 + E

Out of four irreducible representations, 2A1 transforms as z-component while E transforms with x- and y-
components of the dipole moment. Now, owing to two doubly degenerate vibrational modes (E), only three
peaks are expected in the experimental infrared spectrum. However, in the Raman infrared spectrum, four
peaks are expected as all of the irreducible components transform alongside the polarizability tensors.
Similarly, 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 infrared-active; and therefore, only
a single carbonyl stretching is observed in the IR-spectra of the octahedral metal hexacarbonyls. 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 observable infrared-active vibrational modes for some metal
carbonyls are listed in the following below.

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Table 1. The number of IR-active vibrational modes of several prototypical metal carbonyl complexes.

No. of carbonyls Structural prototype (No. of IR-peaks) Structural prototype (No. of IR-peaks)

Three

(1)
(2)

(3) (3)

(2) (3)

Four

(1) (4)

Table 1. Continued on the next page…

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 CHAPTER 11 Metal-Π Complexes: 443

(3)
(4)

(3)

Five

(2)
(3)

Six

(1)

It is worthy to note that these rules apply to metal carbonyls in solution or the gas phase.
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 4. Differentiation of Terminal and Bridging Carbonyl Groups

The mode of attachment of the carbonyl group to the metal center can also be determined by observed
CO stretching frequencies. Terminal carbonyls absorb at the higher wavenumber in comparison to the bridging
ones, which is obviously due to the fact that the extant of backbonding increases with the number of metal
centers. Three main modes of attachment of the carbonyl group with the metal center are:

Terminal µ2-bridging
µ3-bridging

The νCO follows the order: Terminal CO > µ2-bridging > µ3-bridging. The IR-range absorption for various
types of carbonyls groups is listed below.

Table 2. The CO stretching frequencies in different metal carbonyl complexes.

Bonding mode of CO νCO (cm−1)

Free CO 2143

Free CO+ 2184

Terminal CO 2120 - 1850

Symmetric µ2-CO 1860 - 1750

Symmetric µ3-CO 1730 - 1600

For instance, consider the rhodium carbonyl complexes:

Compound µ1-CO, νCO (cm−1) µ2-CO, νCO (cm−1) µ3-CO, νCO (cm−1)

Rh2(CO)8 2060, 2084 1846, 1862

Rh4(CO)12 2044, 2070, 2074 1886

Rh6(CO)16 2045, 2075 1819

There is also a semi-bridging mode that lies in between bridging and terminal bonding profile and is usually
labeled as asymmetric bridging carbonyls.

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 5. Calculation of CO Bond Order

Owing to the well-known fact that the highest occupied molecular orbital (HOMO) set in carbonyl
ligand is of antibonding nature, a close correlation between the magnitude of backbonding and carbon-oxygen
bond order can easily be established. The vibrational frequency of a bond depends upon the strength of the
bond (which is measured by its force constant), and is given as:

(1)
1 𝑘
𝜈𝐶𝑂 (𝑐𝑚−1 ) = √
2𝜋𝑐 µ

Where k is the force constant and µ is the reduced mass. The physical significance of k is implied in the fact
that it is proportional to the strength of the bond involved. Therefore, any factor that increases the electron
density on CO group will decrease its bond order and its force constant; and the vice-versa is also true. In other
words, the decrease in νCO indicates a decrease in CO bond order while the increase in carbonyl stretching is
associated with increasing CO bond order. For instance, the infrared absorption of free CO occurs at 2143 cm−1
while the metal coordinated CO absorbs generally in the range of 2120-1800 cm−1. This clearly establishes the
fact that metal to ligand back donation does occur which in turn reduces its bond order. Hence, the
accumulation of positive charge or the deficiency of electron density will impart a larger CO bond order than
neutral or ionic carbonyl complexes. Consider the following trend in isoelectronic-isostructural carbonyls.

Compound [Ni(CO)4] [Co(CO)4]1− [Fe(CO)4]2−

νCO (cm−1) 2046 1890 1730

M–C Bond order 1.33 1.89 2.16

C–O Bond order 2.64 2.14 1.85

M–C + C–O Bond order 3.97 4.03 4.01

A similar trend is observed in the case of mixed carbonyls i.e. metal carbonyls having some other
ligands alongside CO group. If the other ligand is electron-withdrawing in nature, it would attract the electron
density from the metal center, which in turn would oppose the metal-carbonyl back bonding, yielding
somewhat higher carbon-oxygen bond order and higher carbonyl stretching frequency. On the other hand, If
the other ligand is electron-donating in nature, it would donate the electron density to the metal center, which
in turn would support the metal-carbonyl back bonding, yielding somewhat lower carbon-oxygen bond order
and lower carbonyl stretching frequency.

Compound [Ni(CO)4] [Ni(PF3)(CO)3] [Ni(PMe3)(CO)3]

νCO (cm−1) 2046 1990 1980

Hence, the bond order of CO in [Ni(PMe3)(CO)3] is definitely lower than in [Ni(PF3)(CO)3] because PMe3 is
a weaker π-acceptor than PF3 ligand.

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 6. Study of Reaction Kinetics in Metal Carbonyls

Infrared spectroscopy is a very useful tool in the determination of reaction kinetics of metal carbonyl
complexes. From Beer’s Lambert Law, we know that the absorbance (A) is related to concentration (c) and
path length (l) of the sample as:

1 (1)
𝐴 = 𝜀𝑐𝑙 = 𝑙𝑜𝑔
𝑇
Where ε is the molar extinction coefficient and T is the transmittance of the solution. Therefore, the rate of
disappearance or appearance of a characteristic infrared absorption band can be used to estimate the rate of
change of concentration for the corresponding reactant or product. In other words, the rate of intensity decrease
in IR peaks of reactant, or the rate of intensity increase in IR peaks of product metal carbonyl is proportional
to the rate of change of concentration; which in turn enable us to record various kinetic parameters from
reaction order to activation energy or rate constants.

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Table of Contents
CHAPTER 1 ..................................................................................................................................... 11
Stereochemistry and Bonding in Main Group Compounds: ........................................................ 11
 VSEPR Theory ................................................................................................................................ 11
 dπ–pπ Bonds .................................................................................................................................... 23
 Bent Rule and Energetic of Hybridization....................................................................................... 28
 Problems .......................................................................................................................................... 42
 Bibliography .................................................................................................................................... 43

CHAPTER 2 ..................................................................................................................................... 44
Metal-Ligand Equilibria in Solution:................................................................................................. 44
 Stepwise and Overall Formation Constants and Their Interactions ................................................ 44
 Trends in Stepwise Constants .......................................................................................................... 46

 Factors Affecting Stability of Metal Complexes with Reference to the Nature of Metal Ion and
Ligand .............................................................................................................................................. 49
 Chelate Effect and Its Thermodynamic Origin................................................................................ 56
 Determination of Binary Formation Constants by pH-metry and Spectrophotometry .................... 63
 Problems .......................................................................................................................................... 68
 Bibliography .................................................................................................................................... 69

CHAPTER 3 ..................................................................................................................................... 70
Reaction Mechanism of Transition Metal Complexes – I: ............................................................ 70
 Inert and Labile Complexes............................................................................................................. 70
 Mechanisms for Ligand Replacement Reactions ............................................................................ 77
 Formation of Complexes from Aquo Ions ....................................................................................... 82
 Ligand Displacement Reactions in Octahedral Complexes- Acid Hydrolysis, Base Hydrolysis .... 86
 Racemization of Tris Chelate Complexes ....................................................................................... 89
 Electrophilic Attack on Ligands ...................................................................................................... 92
 Problems .......................................................................................................................................... 94
 Bibliography .................................................................................................................................... 95
CHAPTER 4 ..................................................................................................................................... 96
Reaction Mechanism of Transition Metal Complexes – II:...................................................... 96
 Mechanism of Ligand Displacement Reactions in Square Planar Complexes ................................ 96
 The Trans Effect .............................................................................................................................. 98
 Theories of Trans Effect ................................................................................................................ 103

 Mechanism of Electron Transfer Reactions – Types; Outer Sphere Electron Transfer Mechanism and
Inner Sphere Electron Transfer Mechanism .................................................................................. 106
 Electron Exchange ......................................................................................................................... 117
 Problems ........................................................................................................................................ 121
 Bibliography .................................................................................................................................. 122

CHAPTER 5 ................................................................................................................................... 123

Isopoly and Heteropoly Acids and Salts: ........................................................................................ 123
 Isopoly and Heteropoly Acids and Salts of Mo and W: Structures of Isopoly and Heteropoly
Anions ............................................................................................................................................123
 Problems ........................................................................................................................................ 152
 Bibliography .................................................................................................................................. 153

CHAPTER 6 ................................................................................................................................... 154

Crystal Structures: ............................................................................................................................... 154
 Structures of Some Binary and Ternary Compounds Such as Fluorite, Antifluorite, Rutile, Antirutile,
Crystobalite, Layer Lattices - CdI2, BiI3; ReO3, Mn2O3, Corundum, Pervoskite, Ilmenite and
Calcite.............................................................................................................................................154

 Problems ........................................................................................................................................ 178

 Bibliography .................................................................................................................................. 179

CHAPTER 7 ................................................................................................................................... 180

Metal-Ligand Bonding: ....................................................................................................................... 180
 Limitation of Crystal Field Theory ................................................................................................ 180
 Molecular Orbital Theory – Octahedral, Tetrahedral or Square Planar Complexes...................... 184
 π-Bonding and Molecular Orbital Theory ..................................................................................... 198
 Problems ........................................................................................................................................ 212
 Bibliography .................................................................................................................................. 213
CHAPTER 8 ................................................................................................................................... 214
Electronic Spectra of Transition Metal Complexes: .................................................................... 214
 Spectroscopic Ground States ......................................................................................................... 214
 Correlation and Spin-Orbit Coupling in Free Ions for 1st Series of Transition Metals ................. 243
 Orgel and Tanabe-Sugano Diagrams for Transition Metal Complexes (d1 – d9 States) ................ 248
 Calculation of Dq, B and β Parameters ......................................................................................... 280
 Effect of Distortion on the d-Orbital Energy Levels ..................................................................... 300
 Structural Evidence from Electronic Spectrum ............................................................................. 307
 Jahn-Tellar Effect .......................................................................................................................... 312
 Spectrochemical and Nephelauxetic Series ................................................................................... 324
 Charge Transfer Spectra ................................................................................................................ 328
 Electronic Spectra of Molecular Addition Compounds................................................................. 336
 Problems ........................................................................................................................................ 340
 Bibliography .................................................................................................................................. 341

CHAPTER 9 ................................................................................................................................... 342

Magnetic Properties of Transition Metal Complexes: ................................................................. 342
 Elementary Theory of Magneto-Chemistry ................................................................................... 342
 Guoy’s Method for Determination of Magnetic Susceptibility ..................................................... 351
 Calculation of Magnetic Moments ................................................................................................ 354
 Magnetic Properties of Free Ions ................................................................................................... 359
 Orbital Contribution: Effect of Ligand-Field ................................................................................ 362
 Application of Magneto-Chemistry in Structure Determination ................................................... 370
 Magnetic Exchange Coupling and Spin State Cross Over ............................................................ 375
 Problems ........................................................................................................................................ 384
 Bibliography .................................................................................................................................. 385

CHAPTER 10 ................................................................................................................................. 386

Metal Clusters: ...................................................................................................................................... 386
 Structure and Bonding in Higher Boranes ..................................................................................... 386
 Wade’s Rules ................................................................................................................................. 401
  Carboranes ..................................................................................................................................... 407
 Metal Carbonyl Clusters- Low Nuclearity Carbonyl Clusters....................................................... 412
 Total Electron Count (TEC) .......................................................................................................... 417
 Problems ........................................................................................................................................ 424
 Bibliography .................................................................................................................................. 425

CHAPTER 11 ................................................................................................................................. 426

Metal-Π Complexes: ............................................................................................................................ 426
 Metal Carbonyls: Structure and Bonding ...................................................................................... 426
 Vibrational Spectra of Metal Carbonyls for Bonding and Structure Elucidation .......................... 439
 Important Reactions of Metal Carbonyls....................................................................................... 446

 Preparation, Bonding, Structure and Important Reactions of Transition Metal Nitrosyl, Dinitrogen
and Dioxygen Complexes.............................................................................................................. 450
 Tertiary Phosphine as Ligand ........................................................................................................ 463
 Problems ........................................................................................................................................ 469
 Bibliography .................................................................................................................................. 470

INDEX ............................................................................................................................................. 471