Bonding in complexes of d-block

metal ions – Crystal Field Theory.

energy eg
d shell
d-shell
Δ split by
presence
3d sub-shell of ligand
g
donor-atoms
Co3+ ion
in ggas-phase
p t2g
(d6) Co(III) in
complex
 The d-orbitals:
d orbitals: the t2g
th
set
z z z
y y y

dyz x dxy x dxz x

z z
y y
the eg
x x set
d z2 dx2-y2
 Splitting of the d sub-shell in
octahedral coordination
blue = ligand donor
the t2g set atom orbitals the egset

z z z

y y y

x x x
dyz d z2 dx2-
2 y2

the three orbitals of
the t2g set lie between
the ligand donor-atoms
(only dyz shown)
the two orbitals of the eg set lie along the
C t i coordinates,
Cartesian di t andd so are adjacent
dj t
to the donor atoms of the ligands, which
raises the eg set in energy
 Splitting of the d sub-shell in
an octahedral
t h d l complex
l
energy
eg
d-shell
split by
Δ presence
3d sub-shell of ligand
donor-atoms
donor atoms
Co3+ ion
in gas-phase
t2g
(d6) Co(III)
C (III) iin
octahedral
complex
 The crystal field splitting parameter (Δ)
Different ligands produce different extents of splitting between
the eg and the t2g levels. This energy
gy difference is the crystal
y
field splitting parameter Δ, also known as 10Dq, and has units
of cm-1. Typically, CN- produces very large values of Δ, while F-
produces very small values.

energy
eg eg
Δ = 26,600 cm-1 Δ = 15,000 cm-1

t2g
t2g
2
[Cr(CN)6]3- [CrF6]3-
 High and low-spin complexes:
The d-electrons
Th d l t in
i d4 to
t d8 configurations
fi ti can bbe hi
high-spin,
h i where
h th
they
spread out and occupy the whole d sub-shell, or low-spin, where the t2g
level is filled first. This is controlled by whether Δ is larger than the spin-
pairing
i i energy, P P, which
hi h iis th
the energy required
i d tto ttake
k pairs
i off electrons
l t
with the same spin orientation, and pair them up with the opposite spin.

Paramagnetic
eg 4 unpaired e’s
eg
energy
Δ>P diamagnetic
no unpaired e’s Δ<P

t2g t2g
low-spin
low spin d6 high-spin
high spin d6
electrons fill the t2g level first. In this electrons fill the whole d sub-
case the complex is diamagnetic shell according to Hund’s rule
 High and low-spin complexes of d5 ions:

For d5 ions P is usually very large, so these are mostly high-spin. Thus,
Fe(III) complexes are usually high-spin, although with CN- Δ is large enough
that [Fe(CN)6]3- is low spin: (CN- always produces the largest Δ values)

[Fe(CN)6]3- Δ = 35,000 cm-1 [Fe(H2O)6]3+ Δ = 13,700 cm-1

P = 19,000 cm-1 P = 22,000 cm-1

eg Paramagnetic
P ti
5 unpaired e’s eg
energy
Δ>P paramagnetic Δ<P
one unpaired e

t2g
low-spin
low spin d5 ([Fe(CN)6]3-)
electrons fill the t2g level first. In this
case the complex is paramagnetic
t2g
high-spin
high spin d5 ([Fe(H2O)6]3+)
electrons fill the whole d sub-shell
according to Hund’s rule
 High and low-spin complexes of d7 ions:
The d7 metal ion that one commonly encounters is the Co(II) ion ion. For metal
ions of the same electronic configuration, Δ tends to increase M(II) < M(III) <
M(IV), so that Co(II) complexes have a small Δ and are usually high spin.
The (III) ion Ni(III) has higher values of Δ, and is usually low-spin.
low spin.
[Ni(bipy)3]3+ [Co(H2O)6]2+ Δ = 9,300 cm-1

eg Paramagnetic
P ti
3 unpaired e’s eg
energy
Δ>P paramagnetic Δ<P
one unpaired e

t2g
low-spin
low spin d7 ([Ni(bipy)3]3+)
The d-electrons fill the t2g level first,
and only then does an electron
occupy the eg level.
t2g
high-spin
high spin d7 ([Co(H2O)6]3+)
electrons fill the whole d sub-shell
according to Hund’s rule
 High and low-spin complexes of some d6 ions:
For d6 ions Δ is very large for an M(III) ion such as Co(III),
Co(III) so all Co(III)
complexes are low-spin except for [CoF6]3-.high-spin. Thus,
Fe(III) complexes are usually high-spin, although with CN- Δ is large enough
that [Fe(CN)6]3- is low spin: (CN- always produces the largest Δ values)

[Co(CN)6]3- Δ = 34,800 cm-1 [CoF6]3- Δ = 13,100 cm-1

P = 19,000 cm-1 P = 22,000 cm-1
eg Paramagnetic
eg
4 unpaired e’s
energy
Δ >> P diamagnetic Δ<P
no unpaired e’s

t2g
low-spin
low spin d6 ([Co(CN)6]3-)
electrons fill the t2g level first. In this
case the complex is diamagnetic
t2g
high-spin
high spin d5 ([CoF6]3-)
electrons fill the whole d sub-shell
according to Hund’s rule
 The spectrochemical series:

One notices that with different metal ions the order of

increasing Δ with different ligands is always the same.
Thus, all metal ions produce the highest value of Δ in
their hexacyano complex, while the hexafluoro complex
always produces a low value of Δ. One has seen how in
this course the theme is alwaysy a search for ppatterns.
Thus, the increase in Δ with changing ligand can be
placed in an order known as the spectrochemical series,
which in abbreviated form is:

I- < Br- < Cl- < F- < OH- ≈ H2O < NH3 < CN-
 The spectrochemical series:
The place of a ligand in the spectrochemical series is determined
largely by its donor atoms. Thus, all N-donor ligands are close to
ammonia i iin th
the spectrochemical
t h i l series, i while
hil allll O
O-donor
d liligands
d
are close to water. The spectrochemical series follows the positions
of the donor atoms in the periodic table as:

C N O F
?
P S Cl
very little spectrochemical
data on series follows
S-donors
S donors ≈
P-donors – Br arrows around
between Br
may be higher starting at I and
and Cl
than N-donors ending at C
I
 The spectrochemical series:
Thus, we can predict that O-donor ligands such as oxalate or
acetylacetonate will be close to water in the spectrochemical series.
It should be noted that while en and dien are close to ammonia in
the spectrochemical series, 2,2’bipyridyl and 1,10-phenanthroline
are considerably higher than ammonia because their sp2 hybridized
N-donors are more covalent in their bonding than the sp3 hybridized
donors of ammonia.
O O H3C CH3
- - O O- H 2N NH2
O O
oxalate acetylacetonate en

H 2N N NH2
H N N N N

dien bipyridyl 1,10-phen

 The bonding interpretation of
th spectrochemical
the t h i l series:i
For the first row of donor atoms in the p
periodic table,
namely C, N, O, and F, it is clear that what we are
seeing in the variation of Δ is covalence. Thus, C-donor
g
ligands such as CN- and CO p produce the highest
g values
of Δ because the overlap between the orbitals of the C-
atom and those of the metal are largest.
For the highly electronegative F- ion the bonding is very
ionic, and overlap is much smaller. For the heavier donor
atoms, one might expect from their low electronegativity,
more covalent bonding
bonding, and hence larger values of Δ.Δ It
appears that Δ is reduced in size because of π–overlap
from the lone pairs on the donor atom, and the t2g set
orbitals which raises the energy of the t2g set,
orbitals, set and so
lowers Δ.
• The study of metalloproteins is made easier due to the presence
and p
properties
p of the metal itself. Most metal ion complexes
p are
colored.

• Much of the chemistry of the transition metals results from the

coordination of various ligands to the metal’s d-orbitals. In Crystal
Field Theory this interaction can be viewed as being purely ionic.
 Octahedral Coordination
• Imagine six ligands approaching a metal ion to form an Oh complex.
Assume that the six approach the metal along the x, y, and z axes.

• Under these conditions, the ligands will interact most strongly with
the dx2-y2 and dz2 orbitals.
• These two orbitals (designated eg) will increase in energy; imagine
the lone pairs of the ligand interacting with the electron density in the
d-orbitals.
• The remaining three orbitals (designated t2g) will decrease in energy
energy.
• The difference in energy between the t2g and eg orbitals is defined
as “10Dq”.
 Square Planar Coordination
• If we start with Oh coordination and then “remove” the 2 ligands along the z-
axis, a square planar coordination is achieved.

Oh Sq Pl

• Only metals with eight d-electrons form square planar complexes.

• Note: xy → x2-y2 = 10Dq.

─ ─
─ ─
─ ─
─ ─ ─ ─
 Tetrahedral
et a ed a Coo
Coordination
d at o
• Next imagine eight ligands approaching the
five d-orbitals from along the corners of a
cube.
b
• In this case the ligands don’t approach directly
any of the d-orbitals, but do come closest to
th t2g orbitals,
the bit l thus
th d destabilizing
t bili i ththem. Thi
This
would represent cubic symmetry.
• The energy level diagram for tetrahedral
symmetry t is
i qualitatively
lit ti l similar
i il tto cubic
bi
symmetry, but 10Dq is only half as large.
• 10Dq for tetrahedral complexes is 4/9 of the
octahedral
t h d l case.
 Octahedral Coordination
• What happens when 1 electron is added to the Oh metal orbitals?
goes in a t2g orbital and, therefore, d1 is stabilized byy -4Dq.
– it g q ─ ─
─ ─ ─
• A second electron will also go into a t2g orbital (won’t pair).
– thus, d2 is stabilized by -8Dq.
8Dq. ─ ─
─ ─ ─
• A third electron will also go into a t2g orbital.
– thus,
thus d3 is stabilized by -12Dq.
-12Dq
─ ─
─ ─ ─

• Note now that the t2g

2 orbitals are half filled
filled. If we add a fourth
electron there are two places it can go.
─ ─ ─ ─
─ ─ ─ ─ ─ ─
• Which is more stable? Answer: Depends.
A Comparison
p of the Weak Field and Strong
g Field Cases
─ ─
─ ─
─ ─ ─ ─ ─ ─
10Dq < P 10Dq > P
high spin case low spin case
 Measuring 10Dq
• Look at, for example, Ti(H2O)6+3.
─ ─
– Ti+3 is a d1 ion. 10Dq = 240 KJ/mole
– Say this ion absorbs a photon of
─ ─ ─
appropriate energy to allow transition to
the eg level. What can you say about the
energy off thi
this photon?
h t ? Ephoton
h t = hνh =
10Dq.
– The wavelengths of these photons are
mostly in the UV and visible ranges.
Therefore, can use spectrophotometer to
determine λmax, and from that the
energy.
λmax
– Here λmax = 500nm
– Notice that this is in the visible range.
 Factors
acto s Affecting
ect g Pairing
a g Energies
e g es a
and
d 10Dq.
0 q

• Metals in Oh coordination have the potential to be either high or low

spin. if 10Dq > P then low spin
10Dq < P then high spin

• So, it is important to be aware of factors affecting P and 10Dq.

1 Pairing Energy a result of:

1.
a. inherent repulsion of “forcing” two electrons to occupy the same orbital;
this energy more or less constant from one metal to another.
b energy which is required as electrons with parallel spins are forced to
b.
“flip” in order to pair (a.k.a. exchange energy).

– Pairing energies tend to fall in a fairly narrow range (~230

( 230 – 280
KJ/mole).
 Factors
acto s Affecting
ect g Pairing
a g Energies
e g es a
and
d 10Dq
0 q
2. 10Dq affected by:

a. Oxidation state of the metal; as the oxidation number increases, so does

10Dq. Can justify this in terms of the ligand field model. The increased
positive charge on the metal will bring the ligands in towards it, thus
destabilizing the eg orbitals.
 Factorss Affecting
Facto ect g Pairing
Pa g Energies
e g es and
a d 10Dq
0 q
2. 10Dq affected by:

b. Number and geometry of the ligands; the splitting in Oh field ~9/4 times that in Td
field. Due to 1/3 fewer ligands in Td case (will decrease the field by
33.3%) and the fact that the ligands are not overlapping with orbitals as
much as in the Oh case.
 Factorss Affecting
Facto ect g Pairing
Pa g Energies
e g es and
a d 10Dq
0 q
2. 10Dq affected by:
c. Nature of the ligands. Table 16.2 shows 10Dq’s for
various Cr(III) complexes.
complexes Note that as the ligands
change, so does 10Dq. Table 9.7 shows 10Dq values
for a number of metals with a number of ligands.
Notice that although the absolute values of the 10Dq’s
are different, the trend of the effect that a ligand has
on a metal ion is the same from metal to metal.

Cr(III): Cl- < dtp < F- < H2O < NH3 < en < CN

Co(III): dtp < H2O < NH3 < en < CN

Rh(III): Cl- < dtp < H2O < NH3 < en < CN

Ir(III): Cl- < dtp < NH3 < en

 Factors Affecting Pairing and 10Dq
2. 10Dq affected by:
c. Nature of the ligands.
– If the ligands are listed in order of increasing field strength, a
spectrochemical
p series is obtained.
I- < Br- < Cl- < dtp < F- < OH- < H2O < NH3 < en < CN < CO
weak field strong field

– Although no one metal could be used to derive this series,

series overlapping
sequences can be used.

dd. N
Nature off the
h metal.l
– across the periodic table, no large change, but down the table 10Dq
increases significantly (3d < 4d < 5d).
– result of this is that most complexes of the 2nd and 3rd transition series
are low spin.
Factors effecting spin state

ƒ Both ∆ and the spin pairing energy depend upon the

metal and the ligands.
ligands
- High field ligands, CN- etc, high metal
oxidation
o d o sstate,, andd metalss fromo the 4dd andd 5d
series all favor large ∆ and hence the formation
of low spin complexes
ƒ Tetrahedral complexes can also in principle occur in high
and low spin forms.
- As
A ∆t isi always
l lless th
than ∆o, other
th things
thi
being equal, nearly all tetrahedral complexes are
high spin
Experimental methods for determining
the spin state
‰ Th
The spin
pi state
t t off a complex
pl influences
i fl both
b th the
th
absorption spectrum and the magnetic properties of
the species
‰ Absorption spectra are usually harder to interpret than
magnetic data
‰ Both the orbital and spin angular momenta of the
electrons influence the magnetic properties of a
samplel
- But in coordination complexes the orbital
contribution can often be ignored
 Magnetic Properties of Coordination
Compounds and Crystal Field Theory.

Paramagnetism illustrated:
Interpreting magnetic measurements
ƒ Th
The magnetic i susceptibility
ibili ((χ)) is
i measuredd as a function
f i off
temperature
ƒ A magnetic
g moment (µ) for each metal ion can be obtained from
the magnetic susceptibility
- We can think of the unpaired electrons on each atom as
b h i lik
behaving like a lilittle
l bbar magnet. Th The magnetic
i moment off an
atom or ion is a measure of how strong this bar magnet is.
ƒTTheoretically,
eo et ca y, foro spin sp only
o y systems [S(S )]1/2 µB
syste s µ = 2 [S(S+1)]
- µB (Bohr magneton) are the units in which the
magnetic moment (µ) is given
- S iis the
h totall spin i angular
l momentum. It tells ll you h
how
many unpaired electrons there are
S = 0.5n, where n is the number of parallel spin
unpaired electrons in the ion
Magnetic
g properties
p p
ƒ Magnetic susceptibility measurements can be used to
tell if a complex is high or low spin
ƒ They can also be used to distinguish between square
planar and tetrahedral ggeometries. Square
p q planar
p
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 NiCl422- (tetrahedral) is paramagnetic
 Color and the Colors of Complexes

• Primaryy colors:
– Red (R), green (G) and blue (B).
• Secondary colors:
– Produced by mixing primary colors.
• Complementary
C l colors:
l
– Secondary colors are complementary to primary.
– Cyan (C), yellow (Y) and magenta (M)
– Adding a color and its complementary color
produces white.
Color and the Colors of Complexes
Effect of Ligands
g on the Colors of
Coordination Compounds
Colors

ƒ The colors of most transition metal complexes

arises as a consequence of the ligand field splitting
Electronic spectra

ƒ T
Transition metall complexes
l with
h more than
h one d
electron often show absorption bands at multiple
wavelengths
– not just one transition corresponding to ∆
ƒ The appearance
pp of multiple
p bands is due to electron-
electron repulsion
– may have more than one state for a given
electron configuration
 Crystal Field Stabilization
E
Energy (CFSE)
(CFSE):
When splitting
p g of the d sub-shell occurs, the occupation
p
of the lower energy t2g level by electrons causes a
stabilization of the complex, whereas occupation of the
eg level causes a rise in energy
energy. Calculations show that
the t2g level drops by 0.4Δ, whereas the eg level is raised
by 0.6Δ. This means that the overall change in energy,
the CFSE,
CFSE will be given by:

CFSE = Δ(0.4n(t
Δ(0 4n(t2g
2 ) - 0 6n(eg))
0.6n(e

where n(t
( 2g) and n((eg) are the numbers of electrons in
the t2g and eg levels respectively.
 Calculation of Crystal Field
St bili ti E
Stabilization Energy (CFSE)
(CFSE):
The CFSE for some complexes
p is calculated to be:

[Co(NH3)6]3+: [Cr(en)3]3+

energy
eg eg

t2g t2g
Δ = 22,900 cm-1 Δ = 21,900 cm-1

CFSE = 22,900(0.4
, ( x 6 – 0.6 x 0)) CFSE = 21,900(0.4
, ( x 3 – 0.6 x 0))

= 54,960 cm-1 = 26,280 cm-1

 Crystal Field Stabilization Energy
(CFSE) off d5 andd d10 ions
i :
The CFSE for high-spin d5 and for d10 complexes is
calculated to be zero:

[Mn(NH3)6]2+: [Zn(en)3]3+
energy
eg eg

t2g t2g
Δ = 22,900 cm-1 Δ = not known

CFSE = 10,000(0.4
, ( x 3 – 0.6 x 2)) CFSE = Δ(0.4
( x 6 – 0.6 x 4))

= 0 cm-1 = 0 cm-1
 Crystal Field Stabilization Energy
(CFSE) off d0 to
t d10 M(II) ions:
i

For M(II) ions with the same set of ligands

ligands, the variation of Δ is not large
large.
One can therefore use the equation for CFSE to calculate CFSE in terms of
Δ for d0 through d10 M(II) ions (all metal ions high-spin):

Ca(II) Sc(II) Ti(II) V(II) Cr(II) Mn(II) Fe(II) Co(II) Ni(II) Cu(II) Zn(II)
d0 d1 d2 d3 d4 d5 d6 d7 d8 d9 d10

CFSE: 0 0.4Δ 0.8Δ 1.2Δ 0.6Δ 0 0.4Δ 0.8Δ 1.2Δ 0.6Δ 0

This pattern of variation CFSE leads to greater stabilization in the complexes

of metal ions with high CFSE, such as Ni(II), and lower stabilization for the
complexes of M(II) ions with no CFSE, e.g. Ca(II), Mn(II), and Zn(II). The
variation in CFSE can be compared with the log K1 values for EDTA
complexes on the next slide:
 Crystal Field Stabilization Energy (CFSE) of
d0 to d10 M(II)
( ) ions:

CFSE as a function of no of d-
electrons

1.4
Ni2+
2
SE in multiiples of Δ

1.2
double-
1 humped
08
0.8 curve
0.6
0.4
CFS

0.2
Ca2+ Mn2+ Zn2+
0
0 1 2 3 4 5 6 7 8 9 10 11
no of d-electrons
 Log K1(EDTA) of d0 to d10 M(II) ions:

log K1(EDTA) as a function of no of d-

electrons
= CFSE
20
double-
18 h
humpedd
logK1((EDTA).

curve
16
Zn2+
14
Mn2+ rising baseline
12 due to ionic
Ca2+ contraction
10
0 1 2 3 4 5 6 7 8 9 10 11
no of d-electrons
 Log K1(en) of d0 to d10 M(II) ions:

log K1(en) as a function of no of d-

electrons
= CFSE

12
10 double-
double
humped
1(en).

8 curve
logK1

6
Zn2+
4
rising baseline
2 Ca2+ Mn2+ d to
due t ionic
i i
contraction
0
0 1 2 3 4 5 6 7 8 9 10 11
no of d-electrons
 Log K1(tpen) of d0 to d10 M(II) ions:

log K1(tpen) as a function of no of d-

electrons

20 double-
double
humped
logK1(ttpen).

15 curve
Zn2+
10
Mn2+ N N N N
5 tpen N N
Ca2+
0
0 1 2 3 4 5 6 7 8 9 10 11
no of d-electrons
 The Irving-Williams Stability Order:

Irving and Williams noted that because of CFSE, the log

K1 values for virtually all complexes of first row d-block
metal ions followed the order:

Mn(II) < Fe(II) < Co(II) < Ni(II) < C

Cu(II)
(II) > Zn(II)

We see that this order holds for the ligand EDTA EDTA, en
en,
and TPEN on the previous slides. One notes that Cu(II)
does not follow the order predicted by CFSE, which
would
ld h
have Ni(II) > CCu(II).
(II) Thi
This will
ill b
be di
discussed
d under
d
Jahn-Teller distortion of Cu(II) complexes, which leads to
additional stabilization for Cu(II)
( ) complexes
p over what
would be expected from the variation in CFSE.