chapter 4. molecular symmetry - knubh.knu.ac.kr/~leehi/index.files/coordination_chemistry...valence...
TRANSCRIPT
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Coordination Chemistry II: Bonding 10
dz2, dx2-y2
dxy, dyz, dzx
t2g
eg
dz2, dx2-y2
dxy, dyz, dzx t2
e
Dt
dx2-y2
dxy
dz2
dyz, dzx
eg
a1g
b1g
b2g
dx2-y2
dxy
dz2
dyz, dzx
eg
a1g
b1g
b2g
D1
D2
D3
d Do
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Experimental Facts Thermodynamic Data
[Fe(H2O)6]3+ + SCN- (aq) [FeSCN(H2O)5]
2+ + H2O
[Cu(H2O)6]2+ + 4NH3 (aq) [Cu(NH3)4(H2O)2]
2+ + 4H2O
stability constant (formation constant), K
K1 = [Fe3+][SCN-]
[FeSCN2+]
= 9 x 102
K4 = [Cu2+][NH3]
4
[Cu(NH3)42+]
= 1 x 1013
Q) Why is SCN- (or NH3)
more favorable to Fe(III)
(or Cu(II)) than H2O?
Q) Why do Ag(I) and
Cu(II) have the reverse
order of favoring
ligands?
* HSAB
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Experimental Facts Thermodynamic Data
[Cd(H2O)6]2+ + 4 CH3NH2
[Cd(CH3NH2)4(H2O)2]2+ + 4H2O
[Cd(H2O)6]2+ + 2 en [Cd(en)2(H2O)2]
2+ + 4H2O
DHo = -57.3 kJ/mol
K4 = 3.31 x 106
DHo = -56.5 kJ/mol
K2 = 3.98 x 1010
[Ni(CH3NH2)6]2+ + 4 H2O
Ni(OH)2(s) + 6 CH3NH3+ + 4 OH- [Ni(en)3]
2+ Stable in aq soln
Chelate effect: the enhanced affinity of chelating ligands for a metal ion compared to the affinity of a
collection of similar nonchelating (monodentate) ligands for the same metal.
[Cu(H2O)6]2+
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Experimental Facts Magnetic Susceptibility
SQUID (Superconducting QUantum Interference Device)
Gouy method
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Experimental Facts Magnetic Susceptibility
Magnetic Susceptibility (c) = the degree of magnetization of a material
in response to a magnetic field = M/H
Ferromagnetism : T < TC
Antiferromagnetism : T < TN
Paramagnetism : competition between
magnetic and thermal motion
c
T (K) TC TN
paramagnetic
ferromagnetic
antiferromagnetic
TC : Curie Temperature
TN : Neel Temperature
Curie Law : c = C/T
Curie-Weiss Law : c = C/(T-q)
All magnetic materials should have unpaired electrons.
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Experimental Facts Magnetic Susceptibility
Magnetic Susceptibility (c) Gives information of the magnetic moment (m) of a material
m = 2.828 (cT)1/2 mB (mB : Bohr magneton = magnetic moment of a single electron)
Two sources of magnetic moment – spin (S) and angular(L) motions of electrons
spin quantum number orbital (angular momentum) quantum number
mS+L = g [J(J+1)]1/2 mB
Landé g-factor (gyromagnetic ratio) = 1 + J(J+1) + S(S+1) – L(L+1)
mS+L = g [S(S+1) + 0.25L(L+1)]1/2 mB
total angular momentum quantum number
2J(J+1)
When spin-orbit coupling is negligible,
true for most cases except heavy metals such as Lanthanides
Theoretically,
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Experimental Facts Magnetic Susceptibility
mS+L = g [S(S+1) + 0.25L(L+1)]1/2 mB
2
Landé g-factor (gyromagnetic ratio)
= 1 + J(J+1) + S(S+1) – L(L+1)
2J(J+1)
mS = g [S(S+1)]1/2 mB
In most cases, L is effectively quenched,
J = S, L = 0 g = 2,
gfree electron = 2.0023
0 0
1 ½
0 0
1 ½
1 ½
1 ½
Why is L quenched in crystal field ?
Q) Why do the transition metal ions
have so much diversified magnetic
moments (spin states)?
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Experimental Facts Electronic Spectra
Cu(H2O)62+
Co(H2O)62+
Ni(H2O)62+
Fe(H2O)62+
Co(II)
Q) Why such colors?
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Experimental Facts
Why?
Have to know the characteristics of the
bondings and the electronic structures of
the complexes.
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Valence Bond Theory (VBT) : Hybridization. Description of atomic orbital types used to share
electrons or hold lone pairs to form bonds.
Crystal Field Theory (CFT) : Electrostatic approach. Describing the split of d-orbtal energies in crystal
field. No description of bonds.
Ligand Field Theory (LFT) : Molecular orbital (MO) theory approach to describe the bonds and
electronic structures of the transition metal complexes.
Angular Overlap Method : Estimation of the relative magnitude of MOs.
Theories of Bonding and Electronic
Structure of Complexes
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Theories of Bonding and Electronic
Structure of Complexes Valence Bond Theory
(Hybridization)
First attempt of quantum mechanical explanation of chemical bonding
Y = fA(1)fB(2) Y = fA(1)fB(2)+fA(2)fB(1)
Each electron is free to migrate to the other atom.
Probability to find 2e-’s between two nuclei is high.
bonding
Think forming of a bond as Overlap of atomic orbitals
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109.5o
Hybridization : the concept of mixing atomic orbitals to form new hybrid
orbitals suitable for the qualitative description of atomic bonding
properties.
CH4
sp3
four sp3 orbitals
Theories of Bonding and Electronic Structure of Complexes
Valence Bond Theory
(Hybridization)
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HCl
Cl2
C
H
H
H
90o
90o
90o
and one H at not defined position
???
tetrahedral,
4 equivalent bonds
CH4
4H + C H C H
H
H
A s bond centers along the internuclear axis.
s bond
s bond
Theories of Bonding and Electronic Structure of Complexes
Valence Bond Theory
(Hybridization)
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CH4
sp3
s p 3 h y b r i d a . o . s :
C ( s p 3 )
t e t r a h e d r a l s ( s p 3 C
+ 1 s H
)
4 H C
H
H H
H
109.5o
H2O
O s p 3 2 s
2 p
s p 3 h y b r i d i z e d
l o n e p a i r s i n s p 3 a . o . s
O
H
H
s ( s p 3 O
+ 1 s H
) H-O-H
2 p
2 s s p 3 N
3
s ( s p 3 N
+ 1 s H
) N
H H
H
l o n e p a i r i n s p a . o .
s p 3 h y b r i d i z e d
NH3
N
H
H H
Theories of Bonding and Electronic Structure of Complexes
Valence Bond Theory
(Hybridization)
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BF3
sp2
trigonal planar,
3 equivalent bonds
B
H
H H
Theories of Bonding and Electronic Structure of Complexes
Valence Bond Theory
(Hybridization)
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sp2
C2H4
all six atoms lie
in the same plane
s-bond p-bond
A p bond occupies the space above and below the internuclear axis.
Theories of Bonding and Electronic Structure of Complexes
Valence Bond Theory
(Hybridization)
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sp
linear
Theories of Bonding and Electronic Structure of Complexes
Valence Bond Theory
(Hybridization)
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linear
linear
H-C≡C-H
sp
Valence Bond Theory
(Hybridization)
Theories of Bonding and Electronic Structure of Complexes
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dsp3 PCl5
A
B
B
B
B
B A
B
B
B
B
B
trigonal bipyramid
PCl5
Valence Bond Theory
(Hybridization)
Theories of Bonding and Electronic Structure of Complexes
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d2sp3 SF6
A
B
B
B
B
B
B
A
B
B
B
B
octahedral
B
B
Valence Bond Theory
(Hybridization)
Theories of Bonding and Electronic Structure of Complexes
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Hybridization of metal s, p, d orbitals
Metal or Metal Ion (Lewis Acid) + Ligand (Lewis base) => Formation of Complex
Square planar (dsp2)
Pt2+ ([Xe]4f145d8)
PtCl42- : diamagnetic
Ni2+ ([Ar]3d8)
NiCl42- : paramagnetic
Tetrahedral (sp3)
5d 6s
6p
from ligands 5d dsp2 hybrids
6p
4 dsp2 hybrids (abstract figure)
3d 4s
4p
3d
sp3 hybrids
from ligands
4 sp3 hybrids (abstract figure)
Valence Bond Theory
(Hybridization)
Theories of Bonding and Electronic Structure of Complexes
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3d 4s
4p
Octahedral
Co3+ ([Ar]3d6)
[Co(NH3)6]3+ : diamagnetic [CoF6]
3- : paramagnetic
Octahedral
4d
3d d2sp3 hybrids
from ligands 3d
sp3d2 hybrids
4d
from ligands
Valence Bond Theory
(Hybridization)
Theories of Bonding and Electronic Structure of Complexes
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VBT has great importance of developing bonding theory for coodination compounds.
But •It is highly unlikely to use 4d orbital which is high in energy.
•Many electronic spectra (such as charged complexes) are not well explained.
Today, we rarely use it.
Forget VBT
But, don't foget that VBT is still a good subject for exams.
Valence Bond Theory
(Hybridization)
Theories of Bonding and Electronic Structure of Complexes
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• Developed to explain metal ions in crystal called Crystal Field Theory (CFT)
• Also useful for coordination compounds
• Repulsion between d-orbital e- ligand e-
splitting of energy levels of d-orbitals
Ex) dx2-y2 and dxy orbitals in octahedral field
L
L
L
L
L L
L
L
L
L
L
L
bigger repulsion
higher energy level
Theories of Bonding and Electronic Structure of Complexes Crystal Field Theory
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d
free ion
Uniform Field (Spherical Field)
Theories of Bonding and Electronic Structure of Complexes Crystal Field Theory
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d
free ion
Uniform Field (Spherical Field)
Octahedral Field
dz2, dx2-y2
dxy, dyz, dzx
Theories of Bonding and Electronic Structure of Complexes Crystal Field Theory
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d
free ion
Uniform Field (Spherical Field)
Octahedral Field
dz2, dx2-y2
dxy, dyz, dzx t2g
eg
0.6Do
0.4Do
Do (=10Dq)
: ligand splitting
parameter
Theories of Bonding and Electronic Structure of Complexes Crystal Field Theory
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Octahedral Field (Oh)
dz2, dx2-y2
dxy, dyz, dzx
t2g
eg
Uniform Field
Tetragonal elongation (D4h)
dx2-y2
dxy
dz2
dyz, dzx eg
a1g
b1g
b2g
Theories of Bonding and Electronic Structure of Complexes Crystal Field Theory
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Tetragonal compression (D4h)
dx2-y2
dxy
dz2
dyz, dzx eg
a1g
b1g
b2g Octahedral Field (Oh)
dz2, dx2-y2
dxy, dyz, dzx
t2g
eg
Uniform Field
Tetragonal elongation (D4h)
dx2-y2
dxy
dz2
dyz, dzx eg
a1g
b1g
b2g
Theories of Bonding and Electronic Structure of Complexes Crystal Field Theory
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dx2-y2
dxy
dz2
dyz, dzx eg
a1g
b1g
b2g Octahedral Field (Oh)
dz2, dx2-y2
dxy, dyz, dzx
t2g
eg
Uniform Field
Tetragonal elongation (D4h)
dx2-y2
dxy
dz2
dyz, dzx eg
a1g
b1g
b2g
Square-planar field (D4h)
dx2-y2
dxy
dz2
dyz, dzx eg
a1g
b1g
b2g
D1
D2
D3
Theories of Bonding and Electronic Structure of Complexes Crystal Field Theory
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Octahedral Field (Oh)
dz2, dx2-y2
dxy, dyz, dzx
t2g
eg
Uniform Field Cubic Field
dz2, dx2-y2
dxy, dyz, dzx
Theories of Bonding and Electronic Structure of Complexes Crystal Field Theory
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Octahedral Field (Oh)
dz2, dx2-y2
dxy, dyz, dzx
t2g
eg
Uniform Field Cubic Field
dz2, dx2-y2
dxy, dyz, dzx
Tetrahedral Field (Td)
dz2, dx2-y2
dxy, dyz, dzx t2
e
Dt ≈ 4/9 Do
Theories of Bonding and Electronic Structure of Complexes Crystal Field Theory
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Octahedral (Oh)
dz2, dx2-y2
dxy, dyz, dzx
t2g
eg
Uniform Field Tetrahedral (Td)
dz2, dx2-y2
dxy, dyz, dzx t2
e
Dt
dx2-y2
dxy
dz2
dyz, dzx
eg
a1g
b1g
b2g
Square-planar (D4h)
dx2-y2
dxy
dz2
dyz, dzx
eg
a1g
b1g
b2g
D1
D2
D3
d
Tetragonal elongation (D4h)
Do
Theories of Bonding and Electronic Structure of Complexes Crystal Field Theory
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Why are complexes formed in crystal field theory?
Crystal Field Stabilization Energy (CFSE)
or Ligand Field Stabilization Energy (LFSE)
Octahedral Field
t2g
eg
0.6Do
0.4Do
d3 LFSE of d3 in octahedral structure
= (-0.4Do) x 3 = -1.2 Do
LFSE : the stabilization of the d electrons because of the metal-ligand environments
Theories of Bonding and Electronic Structure of Complexes
Crystal Field Theory
: CFSE, LFSE
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Electron
configuration
(Oh)
t2g1 t2g
2 t2g3 t2g
3eg1 t2g
3eg2
t2g4eg
2 t2g5eg
2 t2g6eg
2 t2g6eg
3 t2g6eg
4
t2g1 t2g
2 t2g3 t2g
4 t2g5
t2g6 t2g
6eg1 t2g
6eg2 t2g
6eg3 t2g
6eg4
weak field, strong field ?
LFSE + pairing energy (Pc + Pe)
= -0.6 Do + 3Pe
LFSE + pairing energy (Pc + Pe)
= -1.6 Do + Pc + 3Pe
Pc : Coulombic energy
Pe : Exchange energy (=exchanges
between the same spins at the same energy )
DE = strong field - weak field
= -Do + Pc
DE > 0 weak field (high spin)
DE < 0 strong field (low spin)
Theories of Bonding and Electronic Structure of Complexes
Crystal Field Theory
: CFSE, LFSE
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Ligand Field Stabilization Energies and Spin States (Oh)
Weak field (high spin) Strong field (low spin)
Theories of Bonding and Electronic Structure of Complexes
Crystal Field Theory
: CFSE, LFSE
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What determines ∆? ∆ depends on the relative
energies of the metal ions and ligand orbials and
on the degree of overlap.
Octahedral (Oh)
dz2, dx2-y2
dxy, dyz, dzx
t2g
eg
d Do
Spectrochemical Series for Ligands
CO > CN- > PPh3 > NO2- > phen > bipy > en > NH3
> py > CH3CN > NCS- > H2O > C2O42- > OH-
> RCO2- > F- > N3
- > NO3- > Cl- > SCN- > S2- > Br-
> I-
π acceptor π donor
(strong field ligand) (weak field ligand)
Spectrochemical Series for Metal Ions
(ox # ↑,ᇫ↑)
smaller size and higher charge
(down a group in periodic table, ᇫ↑)
greater overlap between 4d and 5d orbitals and
ligand orbitals, decreasing pairing energy
Pt4+ > Ir3+ > Pd4+ > Ru3+ > Rh3+ > Mo3+ > Mn4+
> Co3+ > Fe3+ > V2+ > Fe2+ > Co2+ > Ni2+ > Mn2+
Theories of Bonding and Electronic Structure of Complexes
Crystal Field Theory
: CFSE, LFSE
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[Co(H2O)]3+ is the only low-spin
agua complex.
Spectrochemical Series for Metal Ions
(ox # ↑,ᇫ↑)
smaller size and higher charge
(down a group in periodic table, ᇫ↑)
greater overlap between 4d and 5d orbitals and
ligand orbitals, decreasing pairing energy
Pt4+ > Ir3+ > Pd4+ > Ru3+ > Rh3+ > Mo3+ > Mn4+
> Co3+ > Fe3+ > V2+ > Fe2+ > Co2+ > Ni2+ > Mn2+
Theories of Bonding and Electronic Structure of Complexes
Crystal Field Theory
: CFSE, LFSE
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Spin States (Oh)
s ½
1
3/2
2
5/2
2
3/2
1
½
0
½
1
3/2
1
1/2
0
1/2
1
½
0
Theories of Bonding and Electronic Structure of Complexes
Crystal Field Theory
: CFSE, LFSE
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Theories of Bonding and Electronic Structure of Complexes
Crystal Field Theory
: CFSE, LFSE
Magnetochemical Series
Measure pyrrole 1H chemical shift in Fe(III)X(TPP) :
useful for distinguishing weak ligads
H
I- > ReO4- (66.7 ppm) > CF3SO3
- (47.9) > ClO4- (27.7)
AsF6- (-31.5) > CB11H12
- (-58.5)
weaker
Full series
(2015)
For weak ligand, admixed (in between S = 5/2 and S = 3/2) states are observed.
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Qualitative observation of LFSE in thermodynamic data (Hydration Enthalpy)
M2+(g) + 6H2O(l) [M(H2O)6]2+ : DHhyd [∝x (= z2/r) in first order]
Theories of Bonding and Electronic Structure of Complexes
Crystal Field Theory
: CFSE, LFSE
Corrected with spin-orbit splittings,
relaxation effect from the contraction of
the metal-ligand distances, and
interelectronic repulsion energy, and
LFSE. But mostly the differences
between the experimental and corrected
values are from LFSE.
: mostly comes
from LFSE
Measured by M2+(g) + 6H2O(l) + 2H+ + 2e-
[M(H2O)6]2+ + H2(g)
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Ligand Field Stabilzation Energies (Td)
dz2, dx2-y2
dxy, dyz, dzx t2
e
Dt
d 0.4Dt
0.6Dt
tetrahedral field
Dt (≈4/9 Do) : all high-spin configuration
d electrons ex electron configurations LFSEs (Dt) Spin States (S)
1 Ti3+ e1 -0.6 ½
2 V3+ e2 -1.2 1
3 Cr3+ e2t21 -0.8 3/2
4 Cr2+ e2t22 -0.4 2
5 Mn2+ e2t23 0 5/2
6 Fe2+ e3t23 -0.6 2
7 Co2+ e4t23 -1.2 3/2
8 Ni2+ e4t24 -0.8 1
9 Cu2+ e4t25 -0.4 ½
10 Zn2+ e4t26 0 0
Theories of Bonding and Electronic Structure of Complexes
Crystal Field Theory
: CFSE, LFSE
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CFT explains
well the magnetic properties
and in some degree the electronic spectra of the complexes.
However, there is no explaination of the bondings.
In other words, the purely electrostatic approach does not allow for the lower
(bonding) molecular orbitals, and thus fail to provide a complete picture of the
electron structures of complexes.
CFT and MO theory combined complete theory
Ligand Field Theory
(Bonding Theory of Transition-Metal Complexes)
Constructring MOs to explain the electronic structure, magnetic
properties, and bondings.
Theories of Bonding and Electronic Structure of Complexes
Ligand Field Theory
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N atomic orbitals => N molecular orbitals
Symmetry match of atomic orbitals
Relative energy of atomic orbitals
3 things to consider to form MOs
Orbital interactions
in Oh complexes
Theories of Bonding and Electronic Structure of Complexes
Ligand Field Theory
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N atomic orbitals => N molecular orbitals
Symmetry match of atomic orbitals
Relative energy of atomic orbitals
3 things to consider to form MOs
|cA| = |cB|
|cA| > |cB| |cA| >> |cB| |cA| = |cB|
|cA| < |cB| |cA| << |cB|
bbaa cc +=Y
Theories of Bonding and Electronic Structure of Complexes
Ligand Field Theory
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Two Primary Influences to Ligand Field
1) Geometries – Oh, Td, D4h ...
2) Types of Ligands – s-donor, p-donor, p-acceptor
s-donor ligands : H-, NH3 ..
M :H M :NH3
p-donor ligands : halides, O2-, RO-, RS-, RCO2- ...
X- M
px
p-acceptor ligands : CO, CN-, NO+, RCN ...
s-donor orbital
C=O M
p-acceptor orbital
Theories of Bonding and Electronic Structure of Complexes
Ligand Field Theory
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Constructing MOs of Transition-Metal Complexes
MLn:
Assume central metal ion, M, has available s,p, and d orbitals : 9 orbitals
Assume ligands, L, have s and p orbitals : 4n orbitals combination of
the 4n orbitals makes s-donor, p-donor, and p-acceptor orbitals
M
s : A1g
px, py, pz : T1u
dz2, dx2-y2 :,Eg
dxy, dyz, dzx : T2g
Oh (ML6) with s-donor ligands
x2+y2+z2
Theories of Bonding and Electronic Structure of Complexes
Ligand Field Theory
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: representations of s-donor orbitals
L
Gs 6 0 0 2 2 0 0 0 4 2
Oh (ML6) with s-donor ligands
M
s : A1g
px, py, pz : T1u
dz2, dx2-y2 :,Eg
dxy, dyz, dzx : T2g
x2+y2+z2
Gs = T1u + Eg + A1g
Theories of Bonding and Electronic Structure of Complexes
Ligand Field Theory
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Oh (ML6) with s-donor ligands
M
s : A1g
px, py, pz : T1u
dz2, dx2-y2 :,Eg
dxy, dyz, dzx : T2g
Gs = T1u + Eg + A1g
electrons from ligands
frontier orbitals
•electrons from d-orbitals
•same splitting pattern and d-
orbital configuration as in CFT
Why are complexes formed
in ligand field theory?
Because of forming bonding
orbitals
Theories of Bonding and Electronic Structure of Complexes
Ligand Field Theory
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Oh (ML6) with s-donor ligands
Symmetry
Adapted
Orbitals
Think about what these
orbitals look like.
Theories of Bonding and Electronic Structure of Complexes
Ligand Field Theory
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Theories of Bonding and Electronic Structure of Complexes
Ligand Field Theory
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Oh (ML6) with p-acceptor, p-donor ligands
M
s : A1g
px, py, pz : T1u
dz2, dx2-y2 :,Eg
dxy, dyz, dzx : T2g : representations of p orbitals
L
Gp 12 0 0 0 -4 0 0 0 0 0
Gp = T1g + T2g + T1u + T2u
Theories of Bonding and Electronic Structure of Complexes
Ligand Field Theory
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Gs = T1u + Eg + A1g
CO (LUMO)
CO (HOMO)
s-donor ligands
p-acceptor +
Gp = T1g + T2g + T1u + T2u Oh (ML6) with p-acceptor, p-donor ligands
Theories of Bonding and Electronic Structure of Complexes
Ligand Field Theory
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Gs = T1u + Eg + A1g
CO (LUMO)
CO (HOMO)
s-donor ligands
p-acceptor +
Gp = T1g + T2g + T1u + T2u Oh (ML6) with p-acceptor, p-donor ligands
metal-to-ligand (M→L) p bonding
= p backbonding
Theories of Bonding and Electronic Structure of Complexes
Ligand Field Theory
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Oh (ML6) with p-acceptor, p-donor ligands
X- M
C=O M
Gp = T1g + T2g + T1u + T2u
Spectrochemical Series for Ligands
CO > CN- > PPh3 > NO2- > phen > bipy > en >
NH3 > py > CH3CN > NCS- > H2O > C2O42- > OH-
> RCO2- > F- > N3
- > NO3- > Cl- > SCN- > S2- > Br-
> I-
π acceptor π donor
(strong field ligand) (weak field ligand)
Metal-to-ligand (ML) p bonding
(p back-bonding)
increases metal-ligand bond strength
(transfer of negative charge away from the metal ion)
Ligand-to-metal (LM) p bonding
decreases metal-ligand bond strength
(more negative charge on the metal ion decrease of
attraction between the metal ion and the ligands)
Theories of Bonding and Electronic Structure of Complexes
Ligand Field Theory
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D4h (ML4) with s-donor ligands (square planar)
M
s : A1g
px, py : Eu
pz : A2u
dz2 : A1g
dx2-y2 :,B1g
dxy : B2g
dyz, dzx : Eg
Gs = A1g + B1g + Eu
: representations of
s-donor orbitals L
Gs 4 0 0 2 0 0 0 4 2 0
: representations of
p║-orbitals
: representations of
p┴-orbitals
G║ = A2g + B2g + Eu
G║ 4 0 0 -2 0 0 0 4 -2 0
G┴ = A2u + B2u + Eg
G┴ 4 0 0 -2 0 0 0 -4 2 0
Theories of Bonding and Electronic Structure of Complexes
Ligand Field Theory
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D4h (ML4) with s-donor ligands (square planar)
M
s : A1g
px, py : Eu
pz : A2u
dz2 : A1g
dx2-y2 :,B1g
dxy : B2g
dyz, dzx : Eg
Gs = A1g + B1g + Eu
dx2-y2
dxy
dz2
dyz, dzx
eg
a1g
b1g
b2g
D1
D2
D3
CFT
Theories of Bonding and Electronic Structure of Complexes
Ligand Field Theory
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D4h (ML4) with s-donor ligands (square planar) Gs = A1g + B1g + Eu
Symmetry
Adapted
Orbitals Think about what these
orbitals look like.
Theories of Bonding and Electronic Structure of Complexes
Ligand Field Theory
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D4h (ML4) with s-donor ligands (square planar)
M
s : A1g
px, py : Eu
pz : A2u
dz2 : A1g
dx2-y2 :,B1g
dxy : B2g
dyz, dzx : Eg
Gs = A1g + B1g + Eu
G║ = A2g + B2g + Eu
G┴ = A2u + B2u + Eg
s-bonding orbitals : ligand s-donor 8 electrons
p-bonding orbitals : ligand p-donor 16 electrons
metal d orbitals
[Pt(CN)4]2-
Theories of Bonding and Electronic Structure of Complexes
Ligand Field Theory
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up and down
depending on
metals and ligands
D1 >> D2, D3 d8 (sq. pl) low-spin always b1g > a1g, eg, b2g
dx2-y2
dxy
dz2
dyz, dzx
eg
a1g
b1g
b2g
D1
D2
D3
CFT
D4h (ML4) with s-donor ligands (square planar)
[Pt(CN)4]2-
[Ni(CN)4]2-: a2u > b1g > a1g > eg > b2g
Theories of Bonding and Electronic Structure of Complexes
Ligand Field Theory
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Td (ML4)
M
s : A1
px, py, pz : T2
dz2, dx2-y2 :,E
dxy, dyz, dzx : T2
: representations of s-donor orbitals
L
: representations of p ligand orbitals
Gs 4 1 0 0 2
Gp 8 -1 0 0 0
Gs = A1 + T2 Gp = E + T1 + T2
Theories of Bonding and Electronic Structure of Complexes
Ligand Field Theory
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Td (ML4)
M
s : A1
px, py, pz : T2
dz2, dx2-y2 :,E
dxy, dyz, dzx : T2
Gs = A1 + T2 with s-donors only
a1 + t2
L4 M ML4
t2
a1
e + t2
1t2
1a1
2t2
e
2a1
3t2
dz2, dx2-y2
dxy, dyz, dzx t2
e
Dt
CFT
Symmetry Adapted
Orbitals
Think about the shapes
of the MOs
Theories of Bonding and Electronic Structure of Complexes
Ligand Field Theory
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Td (ML4)
M
s : A1
px, py, pz : T2
dz2, dx2-y2 :,E
dxy, dyz, dzx : T2
Gs = A1 + T2 with s-donors
Gp = E + T1 + T2
and p-interactions
Theories of Bonding and Electronic Structure of Complexes
Ligand Field Theory
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Ligand Field Model
• No explicit use of energy
• Difficult to use when considering an assortment of ligands or structures with
symmetry other than Oh, D4h, Td.
Angular Overlap Model
• A variation with the flexibility to deal with a variety of possible geometries and
with a mixture of ligands
• Estimates the strength of interaction between individual ligand orbitals and metal
d orbitals based on overlap between them
• Determine the energy level of a metal d orbital and a ligand orbital in a
coordination complex
Theories of Bonding and Electronic Structure of Complexes
Angular Overlap Model
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s-donor interactions
Basic criteria: the strongest s interaction overlap between dz2 and ligand pz (or hybrid) : es
bonding orbitals: stabilized by es
antibonding orbitals: destabilized by es
The magnitudes of other interactions between d-orbitals and ligand s-orbitals: determined relative to es
Theories of Bonding and Electronic Structure of Complexes
Angular Overlap Model
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s-donor interactions
Ex) s-donor interactions
of [M(NH3)6]n+
dz2 : strength of s-interaction
= 1 + ¼ + ¼ + ¼ + ¼ + 1 = 3
dx2-y2 :
strength of s-interaction
= 0 + ¾ + ¾ + ¾ + ¾ + 0 = 3
dxy, dyz, dzx :
strength of s-interaction
= 0 + 0 + 0 + 0 + 0 + 0 = 0
ligand 1,6 orbitals :
strength of s-interaction
= 1 + 0 + 0 + 0 + 0 + 0 = 1
ligand 2, 3, 4, 5 orbitals :
strength of s-interaction
= ¼ + ¾ + 0 + 0 + 0 + 0 = 1
Theories of Bonding and Electronic Structure of Complexes
Angular Overlap Model
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s-donor interactions
Ex) s-donor interactions
of [M(NH3)6]n+
dz2 : strength of s-interaction
= 1 + ¼ + ¼ + ¼ + ¼ + 1 = 3
dx2-y2 :
strength of s-interaction
= 0 + ¾ + ¾ + ¾ + ¾ + 0 = 3
dxy, dyz, dzx :
strength of s-interaction
= 0 + 0 + 0 + 0 + 0 + 0 = 0
ligand 1,6 orbitals :
strength of s-interaction
= 1 + 0 + 0 + 0 + 0 + 0 = 1
ligand 2, 3, 4, 5 orbitals :
strength of s-interaction
= ¼ + ¾ + 0 + 0 + 0 + 0 = 1
stabilization : 12es
destabilization : 0 or (3xn)es
dz2, dx2-y2
dxy, dyz, dzx t2g
eg
Do CFT
Angular overlap model: not a
complete picture of MOs, but
can estimate the energy levels of
the orbitals
Theories of Bonding and Electronic Structure of Complexes
Angular Overlap Model
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p-acceptor interactions
Theories of Bonding and Electronic Structure of Complexes
Angular Overlap Model
Basic criteria: the strongest p interaction overlap between dxz and ligand p* orbital : ep
ep < es
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p-acceptor interactions
Theories of Bonding and Electronic Structure of Complexes
Angular Overlap Model
Ex) p-acceptor interactions
of [M(CN)6]n-
dz2, dx2-y2 :
strength of p-interaction
= 0 + 0 + 0 + 0 + 0 +0
= 0
dxy, dyz, dzx :
strength of p-interaction
= 0 + 1 + 1 + 1 + 1 + 0
= 4
ligand 1, 2, 3, 4, 5, 6
orbitals :
strength of p-interaction
= 0 + 0 + 0 + 0 + 1 + 1
= 2
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p-acceptor interactions
Theories of Bonding and Electronic Structure of Complexes
Angular Overlap Model
Ex) Energy level diagram of d-orbitals, s-donor and p-acceptor ligands in octahedral complexes
p-acceptor interactions
dz2, dx2-y2 : 0
dxy, dyz, dzx : 4
ligand 1, 2, 3, 4, 5, 6 orbitals : 2
s-donor interactions
dz2, dx2-y2 : 3
dxy, dyz, dzx : 0
ligand 1,2, 3, 4, 5, 6 orbitals : 1
s-donor + p-acceptor interactions
2ep
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p-donor interactions
Theories of Bonding and Electronic Structure of Complexes
Angular Overlap Model
Basic criteria:
same as in p-acceptor interaction : ep
Ex) p-donor interaction of [MX6]n-
dz2, dx2-y2 : strength of p-interaction
= 0 + 0 + 0 + 0 + 0 +0 = 0
dxy, dyz, dzx : strength of p-interaction
= 0 + 1 + 1 + 1 + 1 + 0 = 4
ligand 1, 2, 3, 4, 5, 6 orbitals :
strength of p-interaction = 0 + 0 + 0 + 0 + 1 + 1 = 2
usually, ep for p-acceptor interation > ep for p-donor interation
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p-donor interactions
Theories of Bonding and Electronic Structure of Complexes
Angular Overlap Model
Ex) Energy level diagram of d-orbitals, s-donor and p-acceptor ligands in octahedral complexes
p-donor interactions
dz2, dx2-y2 : 0
dxy, dyz, dzx : 4
ligand 1, 2, 3, 4, 5, 6 orbitals : 2
s-donor interactions
dz2, dx2-y2 : 3
dxy, dyz, dzx : 0
ligand 1,2, 3, 4, 5, 6 orbitals : 1
s-donor + p-donor interactions
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Theories of Bonding and Electronic Structure of Complexes
Angular Overlap Model
s-donor s-donor
+ p-donor
s-donor
+ p-acceptor
LFT
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Magnitudes of es, ep, and D : depend on both ligands and metals
es, ep
• es > ep
• es , ep ↓ as size of X- ↑
and electronegativity of X- ↓ (bond length increase
metal-ligand interaction decrease)
s-donor
+ p-donor
D = 3es - 4ep generally follows the spectrochemical series.
Theories of Bonding and Electronic Structure of Complexes
Angular Overlap Model
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Magnitudes of es, ep, and D : depend on both ligands and metals
Theories of Bonding and Electronic Structure of Complexes
Angular Overlap Model
Spectrochemical Series for Ligands
CO > CN- > PPh3 > NO2- > phen > bipy > en > NH3
> py > CH3CN > NCS- > H2O > C2O42- > OH-
> RCO2- > F- > N3
- > NO3- > Cl- > SCN- > S2- > Br-
> I-
π acceptor π donor
(strong field ligand) (weak field ligand)
Spectrochemical Series for Metal Ions
(ox # ↑,ᇫ↑)
smaller size and higher charge
(down a group in periodic table, ᇫ↑)
greater overlap between 4d and 5d orbitals and
ligand orbitals, decreasing pairing energy
Pt4+ > Ir3+ > Pd4+ > Ru3+ > Rh3+ > Mo3+ > Mn4+
> Co3+ > Fe3+ > V2+ > Fe2+ > Co2+ > Ni2+ > Mn2+
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Four- and six coordinate preference
Theories of Bonding and Electronic Structure of Complexes
Angular Overlap Model
Angular overlap calculation can provide us with some indication of relative stabilities depending on the
number of d electrons and geometries.
ang
ula
r o
ver
lap e
ner
gy
E = 12x(-es) + 5x(0es) + 2x(3es) = -6es
Oh is favorable. Both sq. pl and Oh are favorable.
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Four- and six coordinate preference
Theories of Bonding and Electronic Structure of Complexes
Angular Overlap Model
Angular overlap calculation can provide us with some indication of relative stabilities depending on the
number of d electrons and geometries.
Strong-field sq. pl is favorable.
Angular overlap calculation gives just an approximate. There are many other factors to get a complete picture.
ang
ula
r o
ver
lap
en
erg
y
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Application to hydration enthalpy
Theories of Bonding and Electronic Structure of Complexes
Angular Overlap Model
M2+(g) + 6H2O(l) [M(H2O)6]2+ :
DHhyd [∝x (= z2/r) in first order]
M2+
Assume -1.8 es per each d electron added
(-0.3 es in the textbook is something wrong)
LFSE
weak field octahedral [M(H2O)6]2+ ang
ula
r o
ver
lap
en
erg
y
+ -1.8 es x number of d electrons
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Other shapes
Theories of Bonding and Electronic Structure of Complexes
Angular Overlap Model
Consideration of both group theory and angular overlap model can be used to determine which d orbitals
interact ligand s orbitals and give estimations of the energy levels of the MOs for geometries other than
octahedral and square planar.
trigonal bipyramidal ML5 (D3h)
M
L
L
L
L
L
M
dz2 : A1'
dx2-y2, dxy : E' dyz, dzx : E''
Gs 5 2 1 3 0 3 Gs = 2A1' + A2'' + E'
d e”
e’
a1’
M ML5
e”
e’
a1’ which one?
5 s-donor ligands
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Other shapes
Theories of Bonding and Electronic Structure of Complexes
Angular Overlap Model
trigonal bipyramidal ML5 (D3h)
M
dz2 : A1'
dx2-y2, dxy : E' dyz, dzx : E''
dx2-y2, dxy: strength of s-interaction = 9/8
dyz, dzx : strength of s-interaction = 0
ligands : strength of s-interaction = 1
dz2 : strength of s-interaction = 2¾
2¾ es
9/8 es
es
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Jahn-Teller Effect
There cannot be unequal occupation of orbitals with identical orbitals. To avoid such unequal
occupation, the molecule distorts so that these orbitals no longer degenerate. In other words, if the ground
electron configuration of a nonlinear complex is orbitally degenerate, the complex will distort to remove
the degeneracy and achieve a lower energy.
d9 (Cu(II))
In Oh, effect on eg orbital is bigger so that Jahn-Teller elongation usually occurs for d9.
(Why ? : think about the directions of the orbitals)
favor
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Jahn-Teller Effect
There cannot be unequal occupation of orbitals with identical orbitals. To avoid such unequal
occupation, the molecule distorts so that these orbitals no longer degenerate. In other words, if the ground
electron configuration of a nonlinear complex is orbitally degenerate, the complex will distort to remove
the degeneracy and achieve a lower energy.
d9 (Cu(II))
[Cu(H2O)6]2+
d(Cu-Oeq) = 1.95 Å
d(Cu-Oax) = 2.38 Å
← [Cu(H2O)6]2+ + NH3 → [Cu(NH3)(H2O)5]
2+ + H2O K1 = 20,000
← [Cu(NH3)(H2O)5]2+ + NH3 → [Cu(NH3)2(H2O)4]
2+ + H2O K2 = 4,000
← [Cu(NH3)2(H2O)4]2+ + NH3 → [Cu(NH3)3(H2O)3]
2+ + H2O K3 = 1,000
← [Cu(NH3)3(H2O)3]2+ + NH3 → [Cu(NH3)4(H2O)2]
2+ + H2O K4 = 200
← [Cu(NH3)4(H2O)2]2+ + NH3 → [Cu(NH3)5(H2O)]2+ + H2O K5 = 0.3
← [Cu(NH3)5(H2O)]2+ + NH3 → [Cu(NH3)6]2+ K6 = very small
[Cu(NH3)6]2+ : difficult to make in aqueous solution. Can be made in ammonical solution.
← [Cu(H2O)6]2+ + 2 en → [Cu(en)2(H2O)5]
2+ + 4 H2O
N
N
OH2
N
N
H2O
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Jahn-Teller Effect
d1 (Ti(III))
favor
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Why?
Next Story
Experimental Facts