CY1101-Chemistry, Inorganic Class Notes (Aug-Nov 2015; NNM)

(Text Book: Inorganic Chemistry, Shriver and Atkins, 5th edition, 2010)

Lect 1: Introduction to Coordination Chemistry (re-capitulation of some basics)

Compounds which consist of d-block transition metal-ions and ligands (neutral or anionic non-
metal species) are referred to as metal complexes or coordination complexes. Transition metal
complexes have incomplete d or f shells in the neutral or cationic states. The d-block metals
consists of 3d elements from Sc to Cu, 4d elements from Y to Ag, and 5d elements from Hf to
Au, and f-block metals consist of lanthanoid elements from La to Lu and actinoid elements from
Ac to Lr. Although Sc and Y belong to the d-block, their properties are similar to those of
lanthanoids. The chemistry of d-block and f-block elements differs considerably. Transition
metal complexes are important in catalysis, materials synthesis, photochemistry, and biological
systems. They display diverse structures, chemical, optical and magnetic properties and
reactivity. In the following sections, some of these aspects of d-block transition metal-ions are
highlighted.

Structures of Metal Complexes

In coordination chemistry, a structure is first described by its coordination number, the

number of ligands attached to the metal (more specifically, the number of donor atoms). The
coordination number and geometry of metal complexes are determined by the size of the central
metal, the number of d-electrons, and steric effects arising from the ligands. Complexes with
coordination numbers between 2 and 9 are known. In particular, 4- to 6-coordination (Figure 1)
are the most stable, electronically and geometrically.

Figure 1. Structure of 4 ~ 6 coordination

Central Metal-ions

Properties of d-block transition metal-ions differ considerably between the first (3d) and the
second series metals (4d), although the differences in properties between the second and the third
series (5d) metals is not obvious. Metallic radii of elements from scandium, Sc, to copper, Cu are
significantly smaller than those of yttrium, Y, to silver, Ag or those of lanthanum, La, to gold,
Au. Further, metal compounds of the first series transition metals are rarely seven co-ordinate.
M(II) and M(III) oxidation states are common among the first (3d) series transition metals (Table
1) and they are generally uncommon in compounds of second and third series metals. Higher
oxidation states in the second and third series transition metals are considerably more stable than
those in the first series transition metals.
Table 1. Some common stable oxidation states of transition metals (3d series)

Sc Ti V Cr Mn Fe Co Ni Cu Zn
3 4 3, 4, 5 3, 6 2,7 2,3 2, 3 2 1, 2 2

Ligands
Ligands are inorganic or organic molecules (neutral or anionic) bonded to the metal ion.
Those ligands with a single ligating atom are called monodentate ligands, and those with more
than one ligating atoms referred to as polydentate ligands, which are also called chelate ligands.
Representative ligands are listed in Table 2.

Aqua ions (ions with water ligands) are very common among compounds of first series
metals but few are known amongst the second and third metal compounds.
Two coordinate linear complexes are almost exclusively found for d 10 metal ions (e.g. Cu+,
Ag+, Au +, Hg2+), such as [Cl-Ag-Cl]- or [H3N-Au-NH3]-. A zero-valent complex [Pd(PCy3)2]
with very bulky tricyclohexylphosphine ligands is also known. Generally, stable 2-coordinate
complexes are known for the late transition metals. These metals can adopt higher coordination
numbers under favorable circumstances. Four coordinate complexes typically have a tetrahedral
or square planar geometry. Square planar geometry is only found when there are electronic
reasons for it. Tetrahedral geometry is often found for steric reasons: Small metal ion and large
ligands. Square planar coordination is rarely encountered for metals that do not have a d8
electron configuration. For 3d metals, this d 8 configuration has to be combined with a π acceptor
ligand (e.g. CO, CN-) to get square planar coordination. For 4d and 5d metals nearly all d8
complexes are square planar irrespective of the ligand. By far the most common six-coordinate
geometry is octahedral, but various distortions of the octahedral geometry (e.g. Jahn-Teller
distortion) can be found. Higher coordination numbers are also possible. Some of the early
transition metals are large enough to accommodate more than six ligands.
Isomerism: The arrangement of the ligands is fixed for a given complex, but in some cases it
is changeable to another stable form (isomer). Isomers are compounds with the same chemical
formula but different structures. There are two types: structural (different bonds) and stereo
(identcial bonds) isomers. Stereo isomers are of two kinds: geometrical (cis-, trans-; fac- & mer-)
and optical isomers. As they have different structures they will have different physical and
chemical properties.
Transition metal-ion complexes not only show different structures but also exhibit colors
(spectra), magnetism and reactivity. In order to understand these properties, which depend on d
electron configurations, understanding of the theory of electronic structure is important.

Lect 2: Bonding in Transition Metal Complexes

Crystal field theory (CFT) is one of the most useful theories to account for the electronic
structure of metal complexes. CFT explains many of the basic physical properties of transition
metal complexes but not all of them. Molecular orbital theory (MOT) is more complex than
crystal field theory, but it allows a more complete explanation of the observed physical
properties. In the following sections, discussions are limited to CFT.
In an isolated gas phase metal atom or ion, the five d-orbitals have different shape and
orientations in space (Figure 2). They have the same energy as one another. These d-orbitals can
be grouped into two sets: e g and t2g. In case of e g (dz2 and dx2-y2) the lobes of orbitals lie on the
Cartesian x, y, and z-coordinate systems; while, in case of t2g, the lobes of orbitals lie in between
the Cartesian x, y, and z-coordinate systems.
Figure 2. The five d-orbitals of transition metal-ion

Figure 3. The change in energy of five d-orbitals in the presence of six ligand orbitals

According to CFT, the ligands are treated as point negative charges and the effect of
repulsion between these charges and the d-electrons on the metal ions changes the energy of
these orbitals. In an octahedral field (Figure 3 & 4), when ligands approach metal-ion, two of the
d-orbitals (eg) point towards the ligands and three of d-orbitals (t2g) point away from the ligands.
Repulsion between the ligand electrons and electrons in the two d-orbitals of eg-set destabilizes
them by 0.6 o, the three d-orbitals of t2g-set stabilizes by -0.4 o (negative sign signify
stabilization). The separation between the two sets of orbitals, t2g and eg, is referred to as crystal
field splitting energy or crystal field stabilization energy (CFSE).
Figure 4. The energy of d-orbitals in presence of octahedral crystal field

The extent of CFSE separation depends on the ligand type, the oxidation state of the metal (+2,
+3 or +4), and position of the metal in the Periodic Table (3d, 4d or 5d). Effect of ligand on
CFSE is given by the spectrochemical series (a list of ligands in order of ligand-field strength).
Ligands with strong pi-acceptor (plus sigma-donor) capabilities are strong-field ligands (e.g.,
CO), those with pi-donor abilities (halides) are weak-field ligands and others with pure sigma-
donor (NH3, H2O) capability are moderate-field ligands:

High oxidation state and the higher position of metal (4d or 5d series) favors large Δo:

For octahedral d1-d 3 metals-ion systems, Hund’s rule predicts that electrons will not pair until
all the t2g orbitals are equally occupied. For d4-d7 systems two situations exist, which are
described below.

High-spin and low-spin complexes

Octahedral complexes with d4, d 5, d6, and d7 electron configurations can in principle be in
high- or low-spin states (Figure 5). For example, in d 4 system, the fourth electron has two
options, it can go in an eg orbital so all four electrons are occupying orbitals singly; this is high-
spin (HS d4). Or it could go into a t2g orbital where it will pair up with another electron; this is
low-spin (LS d4).

Figure 5. ML6 complexes with d 4, d 5, d6, and d7 configurations in high- or low-spin states

Which configuration is preferred? Whether the metal will adopt the high or low spin
configuration is determined by two important parameters: (i) o, CFSE, and (ii) pairing energy
(P). The spin-pairing energy (P) is the increase in energy that occurs when an electron is added to
an already occupied orbital. When the Δ o < P, a high-spin configuration occurs which produces
complexes with the maximum number of unpaired electron spins (Table 3 and 4).

Table 3. Calculated CFSE values for metal-ions with d 1-d10 electron configuration
Conversely, when the Δo > P, a low-spin configuration occurs which produces complexes with
the minimum number of unpaired electron spins. From the Table 3, it is easy to see that
configurations like high-spin d 4 and high-spin d 5 have a very small CFSE value, therefore it is
unlikely they will occur. CFSE for octahedral complexes can be calculated (Table 3) using the
following equation:

CFSE = {-0.4 x n(t2g) + 0.6 x n(eg)}o + mP

Where n(t2g) = number of electrons in t2g orbitals
n(eg) = number of electrons in eg orbitals
m = number of paired electron pairs
P = pairing energy
For select metal complexes, the following Table 4 lists values of pairing energy (P), o, CFSE
and resulting spin-state.

Further, the effects of ligand type, oxidation state of the metal and position of the metal (3d,
4d or 5d) on the magnitude of the CFSE values are illustrated in Table 5.
Accordingly, the octahedral Mn(II) complex with Cl- as a ligand (weak-field) has lesser
stabilization energy (7,500 cm-1) as compared to the same complex with CN- (strong-field),
which is four-times greater (30,000 cm-1), thus making it low-spin. On the other-hand, Co(III)
complexes with almost all the ligands (except F-; [CoF6]3- is high-spin) are low-spin because of
+3 oxidation state; similarly, the analogous Rh(III) complexes are all low-spin because the metal,
Rh is in 4d series.

Lect 3: Magnetic properties. Transition metal-ions and complexes are paramagnetic since
they contain unpaired electrons. Magnetic moment values can be used to tell if a complex is high
or low spin. Magnetic moments can be calculated by magnetic susceptibility measurements. The
formula used to calculate the spin-only magnetic moment can be written in two forms; the first
based on the number of unpaired electrons, n, and the second based on the total electron spin
quantum number, S. Since for each unpaired electron, n=1 and S=1/2 then the two formulae are
clearly related and the answer obtained must be identical.

μso= √n(n+2) B.M. or μ so= √4S(S+1) B.M.

Calculated spin-only magnetic moment values for some Oh complexes are shown in Table 5.
Magnetic moment values can also be used to distinguish between square planar and
tetrahedral geometries. Square planar complexes are nearly always low-spin d8 (diamagnetic). If
a four coordinate compound is paramagnetic it is probably tetrahedral. - e.g. Ni(CN)42- (square
planar) is diamagnetic, but NiCl42- (tetrahedral) is paramagnetic.
Table 5. Calculated spin-only magnetic moments for some
octahedral complexes
Ion d-Configuration μso / B.M.
Ti(III) d 1 (t2g1) √3 = 1.73
V(III) d (t2g2)
2
√8 = 2.83
Cr(III) d 3 (t2g3) √15 = 3.88
4
Cr(II) d high spin (t2g3 e g1) √24 = 4.90
4
Cr(II) d low spin (t2g4) √8 = 2.83
5
Mn(II)/ Fe(III) d high spin (t2g3 e g2) √35 = 5.92
5
Mn(II)/ Fe(III) d low spin (t2g5) √3 = 1.73
6
Fe(II) d high spin (t2g4 e g2) √24 = 4.90
6
Co(III) d low spin (t2g6) 0
7
Co(II) d high spin (t2g5 e g2) √15 = 3.88
7
Co(II) d low spin (t2g6 eg1) √3 = 1.73
8
Ni(II) d (t2g6 e g2) √8 = 2.83
9
Cu(II) d (t2g6 e g3) √3 = 1.73

High spin-low spin equilibrium. Some coordination complexes show a phase transition
from high to low spin as a function of temperature. For example, the ferrous-phenanthroline
complex, [Fe(phen)2(NCS)2] (Figure 6).

Figure 6. Phase transition as a function of temperature with [Fe(phen)2(NCS)2]

This has been used as a means of information storage for prototype smart cards. Transition
presumably occurs because Δo is slightly temperature dependent in the solid state.
Lect 4. Further Consequences of d-Orbital Splitting

The splitting of the d orbitals in a complex has important additional structural consequences.
There are two major kinds of structural effects: structural distortions that are observed for
specific electron configurations and effects on the ionic radius of metal ions with regular
octahedral or tetrahedral geometries. Structural distortions’ arising due to specific electron
configurations is highlighted below.
The Jahn–Teller Effect: A structural distortion due to specific electron configurations is
known as Jahn-Teller Effect. For example, for Cu(II) ions, simple octahedral complexes are not
known. The possible electron configurations for octahedral Cu(II) ions are two kinds, with an
odd number of electron in one of the two eg orbitals (Figure 7a or b). On the other hand for
Ni(II), octahedral complex this situation does not arise (Figure 7c) and hence it will not show
distortions in structures.

Figure 7. (a) and (b) two possible electron configurations for Cu(II) ion in Oh geometry, and (c)
only one kind of electron configuration for Ni(II) in Oh geometry

The Jahn–Teller theorem states that such systems (e.g. Cu2+ ions) are not stable because of the
uncertainty of third electron in occupying between one of the two orbitals of equal energy and
hence they will undergo a distortion that makes the complex less symmetrical and splits the
degenerate states, which decreases the energy of the system (Figure 8). The distortion and
resulting decrease in energy is referred to as the Jahn–Teller effect. If Cu(II) had a normal
octahedral geometry (Figure 8a), all the six ligand (L) would be equidistant from the metal,
which rarely happens because of J-T distortion mentioned above. It often displays elongated or
axial (or Z-out) distortion (Figure 8b); while, compressed (or Z-in) distortion (Figure 8c) is rare.
Figure 8. Jahn-Teller distortions of Cu(II) complexes, (a) Oh field, (b) Z-out distortion, (c) Z-in
distortion.

In principle, Jahn–Teller distortions are possible for many transition-metal ions but in
practice they are significant only for systems with an odd number of electrons in the eg orbitals.

CFT for Tetrahedral and Square Planar Complexes

Tetrahedral complexes are the second most common type. They are favored by weak-field
ligands. For example, the [NiCl4]2− ion is tetrahedral because of the presence of weak-field Cl-
ligands around the metal. Tetrahedral geometry is often found for steric reasons: Small metal ion
and large ligands. Here four ligands form a tetrahedron around the metal ion (Figure 9). If one
imagines a tetrahedral molecule inside a cube with ligands occupying alternate corners and metal
center of the cube, the e-orbitals point towards the axis and the three t2-orbitals point in between
the axis and hence these orbitals are of higher energy, opposite to the octahedral case. Since
tetrahedral is non-centrosymmetric, the symbol ‘g’ has been dropped from the two terms, eg and
t2g. The magnitude of splitting is less as none of the d-orbitals point directly towards the
approaching ligands.
Figure 9. (a) In a tetrahedral complex, none of the five d orbitals points directly at or between the
ligands, (b) the order of orbital energies in a tetrahedral complex is the opposite of the order in
an octahedral complex.

The d-orbitals energy splitting (Δt < 4/9 Δo) (t) is lower (by ~45%) than in the octahedral
case. Because of smaller energy separation between ‘e’ and ‘t2’, most of the tetrahedral
complexes are high-spin in nature.
Four-coordinate complexes can be square planar. Square planar coordination is quite
common for the d8 metal-ions in the 4 th and 5 th periods: Rh(I), Ir(I), Pt(II), Pd(II) and Au(III).
Square planar complexes are very rare for 3d metals. Ni(II) generally forms tetrahedral
complexes. With strong π acceptor ligands such as CO, CN- square planar coordination is
possible for Ni(II). For example, the [Ni(CN)4]2− ion is square planar.
It’s much is easier to understand the splitting of d-orbitals in square planar complexes (Figure
10c), when energy level diagrams in octahedral (Figure 10a) and axially-distorted octahedral
(Figure 10b) field are compared.

Figure 10. Splitting of d-orbitals in square planar field

When the axial distortion in octahedral complex is sufficiently large, it results in a 4-coordinate
square planar geometry with the ligands along the z-axis no longer bonded to the metal. Square
planar geometry achieves much higher stabilization more than twice that of Oh geometry.

Lect 5. Colors of Transition-Metal Complexes

The color of coordination complexes, red, purple, blue, green, yellow, orange, etc arises from
electronic transitions between levels whose spacing corresponds to the wavelengths available in
the visible light. In complexes, these transitions are frequently referred to as d-d transitions
because they involve the orbitals that are mainly d in character (for examples: t2g and eg for the
octahedral complexes and e and t2 for the tetrahedral complexes). The colors exhibited are
intimately related to the magnitude of the spacing between these levels. Since this spacing
depends on factors such as the geometry of the complex, the nature of the ligands, and the
oxidation state of the central metal atom, variation on colors can often be explained by looking
carefully at the complexes concerned. Below are a few examples to illustrate this point.

[Ti(H2O)6]3+ in water is purple in color because the d 1-electron of it can be excited into one
of the empty d-orbitals and absorbs a photo of energy equal to o (Figure 11).

Figure 11. (a) [Ti(H2O)6]2+ ion absorbs light in visible region and produces transition, (b) its
absorption spectrum

It absorbs greenish-blue region of the spectrum, thereby transmitting red and blue light to give a
purple color.
Figure 12. Color wheel to identify the color of metal-ion compound and the color of light it is
absorbing

Color wheel is a useful way to show these relationships (Figure 12). When the wavelength of one
or more colors is absorbed, it is the colors on the opposite side of the color wheel that are
transmitted. For example, plant leaves appear green because the chlorophylls absorb strongly in
the blue wavelengths (about 450 nm) and red wavelengths (about 650 nm) but reflect the green
wavelengths (about 525 nm). Similarly, the solutions of most octahedral Cu(II) complexes are
blue. The visible spectrum for an aqueous solution of Cu (II), [Cu(H2O6]2+, shows that the
absorption band spans the red-orange-yellow portion of the spectrum and green, blue and violet
are transmitted, hence making it appear blue. A comparison of the visible absorption maxima for
a number of cobalt (III) complexes shows the effects of ligands on the d-orbital splitting energy
(CSFE) and hence differences in their colors observed (Table 6).

Table 6. Different colors of Co(III) complexes due to different ligands

Complex-ion Wavelength Color of light Color of complex
of light absorbed
absorbed, nm
[CoF6]3+ 700 red green
[Co(H2O)6]3+ 600 yellow-violet blue green
[Co(NH3)6]3+ 475 blue-violet yellow orange
[Co(CN)6]3- 310 ultraviolet pale yellow

Selection rules

The intensity of colors exhibited by different complexes depends on the metal-ion, kinds of
ligands present, metal oxidation state and its position in the periodic table. The magnitude of
color is governed by the selection rules that govern electronic transitions. There are two
important selection rules: (i) Laporte rule, and (ii) spin selection rule. Any transition in violation
of selection rule is said to be ‘forbidden’, some rules are more forbidden than others.
(i) Laporte Rule: In a molecule or ion possessing a centre of symmetry (for octahedral the ‘g’
symbol refers to center of symmetry), transitions are not allowed between orbitals of the same
parity, for example d to d. In other words, there must be change in parity (l=1), i.e. the orbital
quantum number should differ by 1. The forbidden transitions are s s, d d, p f. etc. The
geometries affected by this rule include octahedral and square-planar complexes. The rule is not
applicable to tetrahedral complexes as it does not contain a center of symmetry, and hence d..d
transitions are Laporte allowed.
(ii) Spin selection rule: The spin cannot change during an electronic transition. Promotion of
an electron can only proceed if the spin orientation is conserved, i.e. s = 0. For example,
[Ni(H2O)6]2+, d 8 system, has two-unpaired electrons (Figure 13a) and the total spin in the
ground-state is, S = 1. In the excited state, the number of unpaired electrons remains the same
and hence the total spin, S = 1. The net change in the spin, between the ground and excited state,
S = 0; so the transition is spin-allowed. On the other-hand, in case of [Mn(H2O)6]2+, d 5 (high-
spin), the net change in the spin, between ground and excited state, S = 1, making it spin-
forbidden (Figure 13b).

Figure 13. Illustration of (a) spin-allowed, and (b) spin-forbidden transitions for Ni(II), & Mn(II)

For some common examples possessing octahedral and tetrahedral geometries, the magnitudes of
colors governed by different selection rules are provided in Table 7.
Table 7. The magnitude of colors and applicable selection rules for some typical examples

Summary
Crystal field theory (CFT) is a bonding model that explains many properties of transition metals
that cannot be explained using valence bond theory. In CFT, complex formation is assumed to be
due to electrostatic interactions between a central metal ion and a set of negatively charged
ligands or ligand dipoles arranged around the metal ion. Depending on the arrangement of the
ligands, the d orbitals split into sets of orbitals with different energies. The difference between
the energy levels in an octahedral complex is called the crystal field splitting energy (Δ o), whose
magnitude depends on the charge on the metal ion, the position of the metal in the periodic table,
and the nature of the ligands. The crystal field stabilization energy (CFSE) is the additional
stabilization of a complex due to placing electrons in the lower-energy set of d orbitals. The spin-
pairing energy (P) is the increase in energy that occurs when an electron is added to an already
occupied orbital. A high-spin configuration occurs when the Δo is less than P, which produces
complexes with the maximum number of unpaired electrons possible. Conversely, a low-spin
configuration occurs when the Δo is greater than P, which produces complexes with the
minimum number of unpaired electrons possible. Strong-field ligands interact strongly with the d
orbitals of the metal ions and give a large Δo, whereas weak-field ligands interact more weakly
and give a smaller Δo. Distortion of an octahedral complex by moving opposite ligands away
from the metal produces a tetragonal or square planar arrangement, in which interactions with
equatorial ligands become stronger. Because none of the d orbitals points directly at the ligands
in a tetrahedral complex, these complexes have smaller values of the crystal field splitting energy
Δt. CFSE explains Jahn-Teller distortion of structures of octahedral complexes. Square planar
geometry is common for metal-ions with d8 configuration in 4th and 5th transition series. The
colors of transition-metal complexes depend on the environment of the metal ion and can be
explained by CFT using spin and Laporte selection rules.