ABC mg7 (1) - Bonding in Complexes - Crystalfieldtheory
ABC mg7 (1) - Bonding in Complexes - Crystalfieldtheory
ABC mg7 (1) - Bonding in Complexes - Crystalfieldtheory
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
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 two orbitals of the eg set lie along the
the t2g set lie between C t i coordinates,
Cartesian di t andd so are adjacent
dj t
the ligand donor-atoms to the donor atoms of the ligands, which
(only dyz shown) 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)
eg Paramagnetic
P ti
5 unpaired e’s eg
energy
Δ>P paramagnetic Δ<P
one unpaired e
t2g t2g
low-spin
low spin d5 ([Fe(CN)6]3-) high-spin
high spin d5 ([Fe(H2O)6]3+)
electrons fill the t2g level first. In this electrons fill the whole d sub-shell
case the complex is paramagnetic 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 t2g
low-spin
low spin d7 ([Ni(bipy)3]3+) high-spin
high spin d7 ([Co(H2O)6]3+)
The d-electrons fill the t2g level first, electrons fill the whole d sub-shell
and only then does an electron according to Hund’s rule
occupy the eg level.
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)
t2g t2g
low-spin
low spin d6 ([Co(CN)6]3-) high-spin
high spin d5 ([CoF6]3-)
electrons fill the t2g level first. In this electrons fill the whole d sub-shell
case the complex is diamagnetic according to Hund’s rule
The spectrochemical series:
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
• 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
─ ─
─ ─
─ ─
─ ─ ─ ─
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
─ ─
─ ─ ─
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
Rh(III): Cl- < dtp < H2O < NH3 < en < CN
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
Paramagnetism illustrated:
Interpreting magnetic measurements
Th
The magnetic i susceptibility
ibili ((χ)) is
i measuredd as a function
f i off
temperature
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.
TTheoretically,
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
Magnetic susceptibility measurements can be used to
tell if a complex is high or low spin
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
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 ∆
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))
[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
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 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:
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:
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:
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:
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.