Bonding: Valence Bond, Crystal Field Theories: Coordination Chemistry

BONDING:
VALENCE BOND, CRYSTAL FIELD THEORIES

Coordination Chemistry
TRAN BUU DANG

HOCHIMINH CITY UNIVERSITY OF EDUCATION
Gary L.Miessler, Inorg Chem 5th ed, Pearson Education, 2014, chapter 9.
Housecroft, Sharpe, Inorg Chem 3rd ed, Pearson Education, 2008, chapter 20.
Valence Bond Theory (VB)
An empty hybrid orbital on the metal centre can accept a pair of electrons from a
ligand to form a σ-bond.
The AOs for hybridization in
an octahedral complex: 3dz2,
3dx2- y2, 4s, 4px, 4py and 4pz
With the electrons from the

ligands included and a
hybridization scheme applied for
an octahedral complex, the
diagram becomes:
Phối tử dùng cặp e tự do để xen phủ với AO d trống của kim loại (đã lai hóa)
Free Fe(III) ion (3d5)
lai hóa trong

For a low-spin octahedral complex
tốc độ phản ứng thế chậm hơn, do lúc lai hóa 3d nhận
ít nhiệt hơn --> bền động học hơn
For a high-spin octahedral complex
lai hóa ngoài
u = căn[n(n+2)]
Free Ni(II) ion (3d8)
For a paramagnetic tetrahedral complex

thuận từ
nghịch từ
For a diamagnetic square planar
complex
For an octahedral complex

Crystal Field Theory (CFT)
The electronic structure of metal ions in
crystals, where they are surrounded by
anions that create an electrostatic field
with symmetry dependent on the crystal
structure.
Oh complexes
L
Spliting energy diagram in an octahedral field
eg
delta O
t2g
Center ion in a Center ion in an

Free center ion spherical field octahedral field
Factors governing the magnitude of

∆oct :
- the identity and oxidation state of
the metal ion
- the nature of the ligands.
Splitting of the d orbitals

in an octahedral crystal field
lớn hơn do LHTĐ
The oxidation state of the metal ion affects splitting energy

ion trung tâm có bán kính, số oxh càng lớn thì delta O càng lớn
<P >P>0
P: năng lượng ghép đôi e
the nature of the ligands affects splitting energy

càng nhiều cặp e tự do xung quanh nguyên tử tạo phức --> phối tử trường yếu
phối tử trường mạnh sẽ có khả năng ghép đôi e
Crystal field stabilization energy (CFSE)
high- and low-spin octahedral complexes
How to calculate CFSE in an octahedral crystal field:
- The crystal field is stabilized by -0.4∆oct when a electron is occupied in

t2g orbitals.
- The energy of CF increases by 0.6 ∆oct when a electron is occupied in

eg orbitals.
- If the number of coupling-electron pairs in octahedral crystal field is

one more than that in a spherical field, CFSE rises by a pairing energy
(P).
Tứ diện luôn tạo phức spin cao

Jahn-Teller distortions
Oh complexes D4h complexes

Jahn-Teller distortions
Cu(II) complexes -
significant Jahn–Teller
effects: elongation of
two bonds  weakening
of some metal– ligand
bonds.
D4h – spare planar complexes
D4h – spare planar complexes: d8 (strong field)
Second and third row metal d8 complexes (Pt(II), Pd(II), Rh(I), Ir(I)) are square planar.
Td – tetrahedral complexes: d0,d5 (highspin), d10, d1,d2
Tetrahedral complexes are almost invariably high-spin.
Colour of complexes
Colour of complexes
Magnetic moment
A paramagnetic substance is that its magnetization increases linearly with the
strength of the externally applied magnetic field at a constant temperature.
The magnetization of a diamagnetic complex decreases linearly with increasing

applied field.
The magnetic moment in terms of S and L is
μ = magnetic moment
g = gyromagnetic ratio (conversion to magnetic moment)
S = spin quantum number = sum of the ms for electrons
L = orbital quantum number = sum of the ml values for an electronic configuration
Magnetic moment
The spin-only magnetic moment
In Bohr magnetons, the gyromagnetic ratio, g, is 2.00023, frequently rounded to 2
n = number of unpaired electrons

CFT : uses and limitations
Simplicity
Structure
Limitation
Magnetic property
Nature of bonding
Electronic property
Colour
BONDING: LIGAND FIELD THEORIES
Coordination Chemistry
TRAN BUU DANG

HOCHIMINH CITY UNIVERSITY OF EDUCATION
Gary L.Miessler, Inorg Chem 5th ed, Pearson Education, 2014, chapter 9.
Housecroft, Sharpe, Inorg Chem 3rd ed, Pearson Education, 2008, chapter 20.
Ligand Field Theory (LFT)
How to sketch the MO diagram of a complex molecule
1. Determine the point group of the molecule.
2. Find the reducible representation for each types of bonds.
3. Find the irreducible representations from the corresponding reducible

representation in step 2.
4. Find the irreducible representations for orbitals of center ion.
5. Overlap the LGOs to the same symmetric orbitals of center ion to form bonds.
6. Sketch the target MO diagram.

Molecular Orbitals for Octahedral Complexes - Oh
Molecular Orbitals for Octahedral Complexes – Oh : σ bonding
The symmetry of σ bond M-L
Гσ = A1g + T1u + Eg
The symmetry of d orbitals in center ion
From the character table:

A1g: O’s AO s or a1g orbitals
T2g: dxy, dxz, dyz t2gorbital
Eg: dz2, dx2-y2 eg orbital
Bonding a1g
Antibonding a*1g
a1g
eg Bonding eg Antibonding e*g

t1u
Bonding t1u
Antibonding t*1u
CFT
LFT
Molecular Orbitals for Octahedral Complexes – Oh : π acceptor
The symmetry of π bond M-L
The symmetry of d orbitals in center ion
From the character table:

A1g: O’s AO s or a1g orbitals
T1u: px, py, pz t1u orbitals
T2g: dxy, dxz, dyz t2gorbital
Eg: dz2, dx2-y2 eg orbital
σ donation -
donates
Π acceptance - places
electron density
electron density in CO
from a bonding
antibonding orbitals.
orbital on CO.
weaken the C-O bond

and to decrease the
energy necessary to
stretch that bond.
MO diagrams of a nitrogen molecule
and a carbon monoxide molecule
Ligand Field Theory
Molecular Orbitals
for Octahedral
Complexes – Oh :
π donor
Only σ donor
∆oct increased < P

∆oct increased > P
Weak field ligand
Strong field ligand
High-spin
Low-spin
σ donor, π donor
σ donor, π acceptor
Ligand Field Stabilization Energy

Bonding: Valence Bond, Crystal Field Theories: Coordination Chemistry

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BONDING:

VALENCE BOND, CRYSTAL FIELD THEORIES

TRAN BUU DANG

With the electrons from the

lai hóa trong

For a high-spin octahedral complex

lai hóa ngoài

For a paramagnetic tetrahedral complex

For an octahedral complex

Center ion in a Center ion in an

Factors governing the magnitude of

Splitting of the d orbitals

lớn hơn do LHTĐ

The oxidation state of the metal ion affects splitting energy

P: năng lượng ghép đôi e

the nature of the ligands affects splitting energy

- The crystal field is stabilized by -0.4∆oct when a electron is occupied in

- The energy of CF increases by 0.6 ∆oct when a electron is occupied in

- If the number of coupling-electron pairs in octahedral crystal field is

Tứ diện luôn tạo phức spin cao

Oh complexes D4h complexes

The magnetization of a diamagnetic complex decreases linearly with increasing

The magnetic moment in terms of S and L is

The spin-only magnetic moment

In Bohr magnetons, the gyromagnetic ratio, g, is 2.00023, frequently rounded to 2

n = number of unpaired electrons

TRAN BUU DANG

1. Determine the point group of the molecule.

2. Find the reducible representation for each types of bonds.

3. Find the irreducible representations from the corresponding reducible

4. Find the irreducible representations for orbitals of center ion.

6. Sketch the target MO diagram.

The symmetry of σ bond M-L

From the character table:

eg Bonding eg Antibonding e*g

From the character table:

weaken the C-O bond

∆oct increased < P

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