CHM 113A: General Inorganic Chemistry

Lecture 4

Apparao Draksharapu
[email protected]
 Recap of Lecture III
1. John-Teller Distortion
2. CFT in Spinels

Z-in Normal Spinels : (AII)tet(BIII2)octO4

Z-out
Inverse Spinels : (BIII)tet(AIIBIII)octO4
3. Magnetism (systems with unpaired electrons)

“Any non-linear molecular system in a degenerate

electronic state is unstable and will undergo
distortion to form a system of lower symmetry and
lower energy thereby removing the degeneracy”
 Magnetic Behavior of Metal Complexes
• Magnetic moment has contributions from spin and orbital angular momentum. A spherical
environment may lead to quenching of the contribution from orbital angular momentum.
• Spin-only magnetic moment survives in all cases and is related to the total number of unpaired
electrons.

S = total spin angular momentum, n = number of unpaired electrons in the complex

 What about Orbital Contribution?
If there is a possibility for contribution from the orbital angular momentum,
Effective magnetic moment

For a given value of the orbital quantum number l, the magnetic quantum number m can
have any values from –l to +l including 0 (zero) and L = ∑m

For d-orbital electrons, l = 2, so, m = 2, 1, 0, -1, -2

If there is only one electron in the d-orbitals, L = 2

For 1st row transition metal ions, effect of L on μ is small and μeff correlate fairly well with
those derived from the spin-only formula.
Comparison of Theoretical and Experimental Value

Calculated spin-only
magnetic moments
with experimentally
observed magnetic
moment data

eg

t2g
d7 LS d7 HS
 Orbital Contributions to Magnetic Moment
• For an electron to contribute to the orbital angular momentum the orbital in which it
resides must be able to transform into an identical and degenerate orbital by a simple
rotation.
• For example, in an octahedral complex the degenerate t2g set of orbitals (dxz, dyx, dyz)
can be interconverted by a 90o rotation.
• However, the orbitals in the eg subset (dz2, dx2-y2) cannot be interconverted by rotation
about any axis as the orbital shapes are different; therefore, an electron in the eg set
may not contribute to the orbital angular momentum.
 For a free Ni(II) ion
Orbital Contributions to Magnetic Moment
• Electrons in the t2g do not always contribute to the orbital angular moment.
• For example, in the d3, t2g3 case, an electron in the dxz orbital cannot by rotation be
placed in the dyz orbital as the orbital already has an electron of the same spin.
For Ni(II) Octahedral Com
Consider a Ni(II)
• Orbital must not be symmetrically occupied. (half-filled or fully filled) complex (d 8)

• Tetrahedral complexes can be treated Forina afree

similar
Ni(II) way
ion with the exception that we fill the
e orbital first, and the electrons in these may not contribute to the angular momentum.
Let’s consider Ni(II) complex d8
For a free Ni(II) ion ForNi(II)
For Ni(II)Octahedral
Oh ComplexComplex ForNi(II)
For Ni(II)Tetrahedral
Td ComplexCom
sider a Ni(II) complex (d8)
on Orbital contribution is zero and magnetic m
is close to the spin only value

Orbital contribution is zero Magnetic moment is higher than

dral Complex andNi(II)
For magnetic moment
Tetrahedral is
Complex the spin only value as there is
close to the spin only value positive orbital contribution
 Magnetic
Magnetic
Orbital Properties
Properties of Coordination
of Coordination
Contributions Complexes
Complexes
to Magnetic Moment
Co(II)
Co(II) d 7 d7
K24CoCl4
K2CoCl [Co(H[Co(H 2O)
2O)6]Cl 2 6]Cl2 High spin
Oh complexes, orbital
moisture
moisture contributions to the
Blue Blue Pink Pink magnetic moment are
heat heat important only for the
configurations

eg t2g1; t2g2 ; t2g4 eg2 and t2g5 eg2

t2
Dt Dt
e Do Do Td complexes, it similarly
shown that configurations
t2g that give rise to an orbital
No orbital
orbital contribution
contribution
contributions are
Magnetic
gnetic moment
moment µ = BM
µ = 3.73 3.73 BM
Orbital
Orbital contribution
contribution
Magnetic
Magnetic momentmoment 4.2 B.M.e2t21, e2t22, e4t24, and e4t25
µ =B.M.
µ = 4.2
higherhigher than spin-only
than spin-only valuevalue
 Consider a Ni(II) with (C.N. = 4)
Consider
Identification of aGeometry
Ni(II) withThrough
(C.N. = 4)Magnetism
What will be the geometry of a diamagnetic Ni(II) complex with
What will beWhat will be the
the coordination
geometry geometry
of anumber 4?of aNi(II)
diamagnetic diamagnetic
complex Ni(II) complex withnumber FOUR?
with coordination
coordination number 4?
• It can not be octahedral
Ans: C.N. =as4;there
henceiscomplex
only fourmust
ligands as the coordination
be tetrahedral or squarenumber
planar. is four.
• It must beAns: C.N.
either
DrawTd=or4;Sp!
the hence
energycomplex
level must be tetrahedral
diagrams and fill theor square planar.
orbitals with
-.
e-.
DrawDiamagnetic
the energyso level diagrams and fill the 8 orbitals
NO unpaired electron. It s8 a d system. with e
Diamagnetic so NO unpaired electron. It s a d system.
Tetrahedral: Square planar:
TetrahedralTetrahedral: SquareSquare
Planarplanar:

6
6
 Ferromagnetism
❑ In a normal paramagnetic material, the atoms containing the unpaired electrons are magnetically
dilute, and so the unpaired electrons in one atom are not aligned with those in other atoms.

❑ However, in ferromagnetic materials, such as metallic iron, or iron oxides such as magnetite (Fe3O4),
where the paramagnetic iron atoms are very close together, they can create an internal magnetic
field strong enough that all the centers remain aligned:
 spontaneous magnetization.
Antiferromagnetism
If the opposing moments balance completely, the alignment is known as
If the opposing moments
• antiferromagnetism. balance antiferromagnets
Therefore completely, the alignment
do notis have
known a as
antiferromagnetism. Therefore, antiferromagnets do not have a spontaneous
spontaneous
magnetization.
magnetization.
Antiferromagnetic materials
• Antiferromagnetic occuroccur
materials commonly among among
commonly transitiontransition
metal compounds,
metal
especially oxides,
compounds, e.g., NiO,oxides,
especially and MnO.
e.g. NiO, MnO.

Antiferromagnetic ordering 17
 Metal mayparamagnetism
show paramagnetism depending on oxidation
statestate and ligands
Metal may
Color of Transition Metal Complexes
show depending on oxidation and ligands

Vanadium metal (center) in solution as

• Transition metal complexesVanadium often 2+
colored
metal (center)
3+
(absorb
in solution
2+
aslight
+
in visible range)
V (aq),V V(aq),
2+ 3+ V VO
(aq), (aq),(aq),
2+ VO (aq),
and VOand2 VO
+
2 (aq),
(aq),
2+ Mn3+2+ Cr3+ V to(aq),
2+
right) V (aq), VO (aq),
3+ 2+
Co2+2+ MnCo2+2+ Cr 3+ Fe 3+ 3+Fe3+ Ni2+
Ni2+ (left to (left
right)
Co Mn Cr Fe Ni2+ and VO2+(aq) [CrIII(NH3)6]3+

[CrIII(NH3)5Cl]2+

• Color
Color is ais a isqualitative
qualitative
Color assay ofassay
a qualitative assay
valence levels of
of valence valence
(electronic
levels levels (electronic structure)
structure)
(electronic structure)
 Color of Transition Metal Complexes
• The colour of a transition metal ion is associated with
(a) Incomplete d level (between 1 and 9 d-electrons)
(b) The nature of the ligands surrounding the ion.
• A complete theory of color is very complex but, put simply, it is due to the movement
of electrons from one electronic level to another.
 because
Color of Transition the high-spin
Metal complex
Complexes
complementary appe
Electronic Spectra of Metal Complexes in color
•
absorbs photons in the
Color absorbed.
Color we observe when we look at an object or a compound is due
we observe red
whentowe light
look at thathigh
is
an object
or a compound is due to light that is
wavelengths
transmitted or reflected, not light that is absorbed. transmitted or reflected, not light that is
• Reflected or transmitted light is complementary in color to Thus a green compound
the
absorbed.
Solution of [Cu(NH ) ]2+ ions absorbs red
light that is absorbed. 3 4 red portion
Reflected or of the
transmitted lightvisible
is
and orange light, so the transmitted light complementary
• Thus a green compound absorbs light in the red portionabsorbed.
in color to the light that is
of versa, as indicated by t
appears as the
the visible complementary
spectrum and vice versa, ascolor, blue
indicated by the color wheel.
complementary color wheel. 2+
Solution of [Cu(NH ) ] ions absorbs red
Thus a green compound absorbs light in the
3 4 red portion of the visible spectrum and vice
[Cr(H 3+
O) light,
and orange ] so the transmitted light
[Cr2III(H62O)6]3+ versa, as indicated by the complementary
appears as the complementary color, blue color wheel.
[Cr(H2O)6]3+

For a photon to effect a transition, its energy

For a photon must
to effect be equalits
a transition, to
the For a photon
difference to effect
in energy between
energy mustthe a dtotransition,
two
be equal orbitals, in its
which
the difference
depends on themust
magnitude energy between the two d orbitals, which Cr
Cr3+3+(aq)
(aq), Fe Fe 3+(aq) 2+ Co2+(aq)
3+(aq), and Co (aq) (left,
energy be of Δo
equal to the difference in
depends on the magnitude of Δo 4
 ColorElectronic
of Transition
Spectra
Electronic Metal
Spectraof
ofMetal
MetalComplexes
Complexes
Complexes

[Fe(H
[Fe O)6]SO4 appears
II(H 2O) appears blue-green
2 6]SO4 blue Low-spiniron(II)
iron(II) appears pale6]
Low-spin complex K4[Fe(CN)
because the high-spin complex
green because the high-spin yellowpale
appears higher-energy
yellow because complex
it absorbs
[Fe(H
[Fe(H2O)
absorbs ]SO4photons
26O)6]SO
appears in blue-green
appears the red
blue-green Low-spin iron(II) complex K4[Fe(CN)
absorbs photons
4
in the red higher-energy
K [FeII(CN)
Low-spin ] violet photons.
because
iron(II) complexit absorbs 6] 6 ]
K4[Fe(CN)
because
because thethe high-spin
wavelengths high-spin complex
complex 4 6
photons. appears
appears pale yellow
pale yellow
high-energy violet because
becauseit absorbs
photons. it absorbs
absorbs
absorbs photonsphotons in in thethe redred higher-energy
higher-energy violet photons.
violet photons.
wavelengths
wavelengths
5
Electronic Spectra of Transition Complexes
Beer-Lambert Law- An Empirical law
𝐼1
𝐴 = − log = − log( 𝑇) = − log( %𝑇/100)
𝐼𝑜

A=ɛCl
A = absorbance
ɛ = molar absorptivity (L/mole/cm)
l = cell pathlength (cm)
C = concentration of analyte (mol/L)
Increasing conc. 5 cm
0.5 cm 1 cm

16
 Inference from the Electronic Spectra
• The color of coordination complexes arises from electronic
transitions between levels who's spacing corresponds to the
wavelengths available in the visible light.
• Number of transitions (multiple d-d transitions are possible)
• Energy of the transitions (position of the band)
• Intensity of the transitions (allowed transitions)
Origin of Shoulder in the Spectrum of [Ti(H2O)6]3+
• Compression removes the
degeneracy and gives more
stabilization energy.

• Elongation doesn't remove

the degeneracy and would
give less stabilization
energy.

From the splitting diagram for the J-T compressed system, instead of one possible transition from
the t2g to the eg, we now have two: from the dxy up to either the dx2-y2 or to the dz2.

This will mean we will get an absorption of light of two different wavelengths, and hence two
peaks, one of which appears as a shoulder on the other.
 Factors that Influence the △
1. Oxidation state of the metal complex
Higher ionic charge on the metal ion, pulls the ligands closer towards it and
higher electrostatic repulsion results in larger splitting of d-orbitals.

2. Coordination number / Geometry of the complex

Tetrahedral complexes ML4 have smaller Δ than octahedral ones (ML6).

3. △ value directly proportional to the size of the metal in a group

Higher the effective nuclear charge and size of the central metal larger the d-
orbitals splitting Large Δ value.

4. Nature of ligands (weak-field vs strong-field ligand)

Stronger the ligand, higher the Δ value.
19
 Origin of the Color
Electronic Intensity
Spectra of Metal Complexes
Electronic Spectra of Metal Complexes
As the oxidation state of the metal increases,
• Oxidation state increases –sosplitting
so also doesof
thed-orbital
amount of energy raises
As the oxidation state of the metal increases,
also does the splittingof of
amount of splitting the
the
d
d
orbitals.
orbitals.
• Ligands (low field vs strong field)
Changes of oxidation state therefore change
• Geometry (Oh vs Td) Changes of oxidation state therefore change
the colour of the light absorbed, and so the
thecolour
colour of light
of the the you
lightsee.absorbed, and so the
colour of the light you see.
of Metal Complexes
es,
ed

ge
he changing the ligand is changing the color
[CrII(H2O)6]2+ [CrIII(H2O)6]3+ [CrIII(OH)6]3- [CrIII(H2O)6]3+ [CrIII(NH3)6]3+ [CoII(H2O)6]2+ [CoIICl4]2-
The difference in the colors is going
to be a combination of the effect of
changing the ligand is changing the color the change of ligand, and the
Oxidation state Ligand strength
https://www.chemguide.co.uk/inorganic/complexions/colour.html Geometry
change of the number of ligands.
6

The difference in the colors is g

to be a combination of the effe
 Electronic Spectra
Electronic of
ElectronicTransition
Spectra
Spectra Metal
of Metal
of Metal Complexes
Complexes
Complexes
• TwoAmong
copperthe
complexes
Among with
the
following
different
following
two
oxidation
two states and
(e.g.,
one is Cu+1one
Cu complexes
Cu complexes
Cu(I)
isanotherand
Cu+1 and Cu(II) given
Cubelow.
Cu+2 canisyou
is another +2 can you identify
identify
Which onebased
them will them
have low
based
on their intensity
on theircolour
color? color?and which one will have high intensity colour?

Copper(I) complexes with d10 configurations such as d9 copper(II) complexes such as Cu(NO3)2·5H2O are
Cu(I)(a)
tend to be(a)colorless
Copper(I)(eg complexes
set filled). To excite
with brightly
an such
d10 configurations
d10 configurations colored.
such
tendasto Octahedral
CuI
betend toCube ecolorless,
2+ have a vacancy in
Copper(I) complexes with as CuI colorless, g orbitalseg orbitals
the level,
eg orbitals, andtheelectrons canphotons
electron to a higher
areexcite
are filled. To level,
filled. such
exciteasan
anToelectron tothe 4p orbital,
electron
a higher to a higher
level, such as thesuch as
4p orbital, 4p orbital,
photons of be
veryexcited to this
of very
high high
photons of very high energy are necessary. This level. The wavelength of the light absorbed
energy areenergy
necessary.are necessary.
This energyThis energy corresponds
corresponds to very
to very short short wavelengths
wavelengths in the ultraviolet
in the ultraviolet
energy corresponds to very short wavelengths in the corresponds to the visible part of the spectrum, and
region of theregion of the spectrum.
spectrum. No visible No lightvisible light is absorbed,
is absorbed, so the eyesosees the no
eyechange,
sees noand change,
the and the
UV region of the spectrum. No visible light is Cu2+ monomeric complexes are almost always
compound
absorbed,
compound
hence,appears appears
white
the compound
whitecolorless.
orappears
colorless. or colorless. colored.
 Factors Affecting Electronic Spectra of
Transition Metal Complexes
• Factors affecting △ (crystal field splitting parameter) also affect electronic spectra.
• Intensity (ℇ) depends on the geometry of complexes due to the modulation of selection rules.
Intensity is related to the “probability” of a transition.
• Nature of the ligand: Variation due to crystal field strength (e.g., spectrochemical series).
• Nature of metal ion, selection rule, and it’s relaxation process.

Selection Rules
LaPorte Selection Rule
• During electronic transition there should not be any change in the orbital angular momentum
(∆l ≠ 0).
• In centrosymmetric environments, transitions can occur only between states of opposite
parity (u → g or g→ u). This means that d → p is allowed but not d → d. Also please note that p
→ f or s → d is not allowed as Δl should be ±1 (l = orbital quantum number).
 LaPorte Selection Rule

• The transitions that occur in Oh complexes are d-d. According to the selection rule, the d-d
transition is forbidden. However, many
Symmetry Oh complexes
(Laporte) exhibit color.
Selection Rules Why?
• This is primarily due to distortion in Oh complexes occurs and hence they lost their symmetry
temporarilyq as thewhy
Then molecule is not static
are octahedral andcoloured?
complexes it vibrates as shown below.
q Again our model is deficient:
• This phenomenon is calledare
Ø molecules vibronic (vibrational-electronic)
not rigid but are always vibrating coupling and can relax the Laporte
selection rule.

During this vibration, centre of

inversion is temporarily lost:
d-p mixing can occur
 Relaxation in LaPorte Selection Rule
• Mixing: π-acceptor and π-donor ligands can mix with the d-orbitals, so transitions are
no longer purely d-d.
• However, the vibrational amplitude is small, so deviation and mixing is small. Hence,
octahedral complexes have lower intensity bands than tetrahedral complexes.
• In tetrahedral complexes, there is no center of symmetry, and thus tetrahedral
geometry is not affected by this rule.
• For tetrahedral complexes, there can be a mixing of d and p orbitals through covalency.
L L
L L
M M
M
L L
L L
A metal p-orbital overlaps A metal d-orbital overlaps
with ligand orbitals with the same ligand orbitals
 Relaxation in LaPorte Selection Rule
• The same way of ‘relaxing’ the orbital selection rule is not available in octahedral
complexes

L L
in phase
L L L L
no overlap
L L L L
out of phase
L L

A metal p-orbital overlaps A metal d-orbital cannot overlap

with ligand orbitals with the same ligand orbitals

In general, no mixing of the ‘d’ and ‘p’ orbitals is possible if the molecule
has a centre of inversion (Laporte rule)
 Case in Point: Td vs Oh Complexes
❑ As we have seen, a tetrahedron has no center of symmetry, and so orbitals in such
symmetry cannot be gerade. Hence the d-levels in a tetrahedral complex are e and
t2, with no ‘g’ for gerade.

❑ This largely overcomes the Laporte selection rules (enabled by d-p mixing), so that
tetrahedral complexes tend to be more intense in color than octahedral.
 Spin Forbidden
Spin-forbidden and Spin
and Spin-allowed Allowed
Transitions Transitions
forbidden and Spin-allowed Transitions
• Transitions can occur only between energy states with the same spin-multiplicity (∆S = 0). Or in
on forother
which words,
ΔS¹≠0anyistransition
strongly for which ΔS that
forbidden; ≠ 0 isis,strongly forbidden;
Spin
in order to that is, to
Selection Rule
be allowed, a be allowed, a
which transition
ΔS¹≠0 is must involve
strongly no change
forbidden; that ininspin
is, state.
order to be allowed, a
ust involve no change in spin state. The overall spin S of a complex must not change dur
olve• no The
change
spininofspin
the state.
complex must not change during the transition.
electronic transition, hence, ΔS = 0.

hυ hυ
ed Forbidden Forbidden

Forbidden Allowed
Allowed Forbidden
[Mn(H2O)6]2+ has a d5 configuration and it is a high-spin complex. E
transitions are both Laporte-forbidden, and spin-forbidden; it is t
d5metal
II(Hion and is a high-spin complex. Electronic transitions
e are
• [Mn O) ]2+ has a d 5 configuration and it is a high-
colorless. g
2+ has a dbutmetal
orbidden, 25 6
also ion and is a high-spin
spin-forbidden. complex.
The dilute solutionsElectronic
of Mn 2+ hυ
transitions are
spin complex. Electronic transitions are - both 2-
aporte-forbidden,
efore colorless. but also MnO4 The
spin-forbidden. and CrO4 are intensely
dilute colored
solutions of even
Mn 2+
though it is d0 system. The
Laporte-forbidden and spin-forbidden; it is
these complexes are not from d-d transitions, but from charge-trans
are therefore colorless.
therefore colorless. t2g
ligand to metal orbitals.
Forbidden
 Predicted values of ℇ

• MnO4- and CrO42- are intensely colored even though it is d0 system. The color of these complexes are
not from d-d transitions, but through charge-transfer from ligand to metal orbitals. 28
 Charge Transfer Bands
• If color is largely dependent on d-d transitions,Charge
why is it that some transition
Transfer Bands metal complexes
Charge
are intensely colored in solutionTransfer
but possess no dBands
electrons?
If color is dependent on d-d transitions, why is it that some transition metal
If color is dependent on d-d transitions, why
complexes are is it that
intensely some
colored transition
in solution metal
but possess no d electrons?
Colors dueare
• complexes to d-d transitions
intensely not
colored inintense
solutioninbut
colour especially
possess with Oh complexes
no d electrons?
Colours due to d-d transitions
Colours due to d-d transitions

Colours due to LMCT (for KMnO4 and K2CrO4)

Colours due to LMCT (for KMnO4 and K2CrO4)

• However, colors due to LMCT

are intense in color!
KClO4 (no suitable energy
KMnOKMnO
4
4 K CrO
K2Cr2 2O44 KClO
d-orbitals for LMCT)4
12
 Ligand toMetal
Ligand to Metal Charge
Charge Transfer
Transfer (LMCT(LMCT)
)
Ligands
• Ligands possess
possess σ, π,
σ, σ*, σ ,π*,
π, π , and
and nonbonding(n)
nonbonding (n)molecular
molecular orbitals.
orbitals. IfIfthe
theligand
ligand molecular
molecular orbitals are full, charge transfer may occur from the ligand molecular
orbitals are full, charge transfer may occur from the ligand molecular orbitals to the empty or
orbitals to the empty or partially filled metal d-orbitals.
partially filled metal d-orbitals.

• This is always possible, but LMCT transitions are usually in the ultraviolet
This is always possible but LMCT transitions are usually in the ultraviolet
• They occur
They in theinvisible
occur or near-ultraviolet
the visible if if
or near-ultraviolet
- Metal is easily reduced (for example metal in high oxidation state)
metal is easily reduced (for example metal in high oxidation state)
- Ligand is easily
ligand oxidized
is easily oxidized 13
 Ligand to Metal Charge Transfer (LMCT)
•
Ligand to Metal Charge Transfer (LMCT
This is always possible, but LMCT transitions are usually in the ultraviolet
)
• They occurThey
in the visible
occur or near-ultraviolet
in the if
visible or near-ultraviolet if metal is easily reduced (for
example metal in high oxidation state)
- Metal is easily reduced (for example metal in high oxidation state)
- Ligand is easily oxidized

TiO2 VO43- CrO42- MnO4-

Ti4+ V5+ Cr6+ Mn7+

d0 in far UV ~39500 cm-1 ~22200 cm-1 ~19000 cm-1

white white yellow purple

more easily reduced

 If the metal is in a low oxidation state (electron rich) and the ligand
Metal to Ligand Charge Transfer (MLCT)
possesses low-lying empty orbitals (e.g., CO or CN ) then a metal-to-
ligand charge transfer (MLCT) transition may occur.
• If the metal is in a low oxidation state (electron rich) and the ligand possesses low-lying empty
orbitals (e.g.,taking
ligands CO or CN−) then a metal-to- ligand charge transfer (MLCT) transition may occur.
part in MLCT include 2,2'-bipyridine (bipy), 1,10-
phenanthroline (phen), CO, CN and SCN
• ligands taking part in MLCT include 2,2'-bipyridine (bipy), 1,10-phenanthroline (phen), CO, CN−
and SCN−

Examples: Origin of color:

W(CO)4(phen)
Fe(CO)3(bipy) 15   10 – 200 M-1 cm-1
d-d transition
Examples: W(CO)4(phen) and Fe(CO)3(bipy)
charge-transfer transition   103 M-1 cm-1