Coordination Chemistry

Coordination Compounds

• A central metal atom bonded to a

group of molecules or ions is a
metal complex.
• The molecules or ions coordinating
to the metal are the ligands.
• They are usually anions or polar
molecules having nonbonding
electrons (lone pairs) to interact
with empty orbital of the metal
M L
 A chemical mystery:
Same metal, same ligands, different number of ions when
dissolved

3
 Werner’s Theory
• metal ions have primary and secondary valences.
– Primary valence equals to the metal’s oxidation number
– Secondary valence is the number of atoms directly bonded to
the metal (coordination number)

4
 Coordination Number
Coordination Number 1

Ion pairs such as Na+Cl- in vapour phase may be considered as

examples of C.N. 1, although NaCl is not a coordination compound.
 Aryl radicals derived from highly sterically hindered
1,3,5-triphenylbenzene

M = Cu, Ag

5
Coordination Number 2

Limited to +1 ions of group 11 and Hg2+ (all are d10).

 [Cu(NH3)2]+, [Ag(NH3)2]+, [CuCl2]-, [Ag(CN)2]-, [Hg(CN)2].

Coordination Number 3

Cl

Cl Cu Cl

Cl

[Hg(SBu')3]-

6
 Coordination Number 4

Tetrahedral (Td)

Favored by
 Ligands like Cl-, Br-, I-, O2- etc.
 Metal ions with noble gas configuration (ns0, Be2+)/pseudo-noble gas
configuration (n-1)d10 ns0 np0 (Zn2+, Ga3+)/group oxidation state.
 Transition metals with low CFSE.
 [MnO4]-, [CrO4]2-, [Ni(CO)4], [Cu(Py)4]+, [Zn(NH3)4]2+.

7
 Coordination Number 4

Square Planar (D4h)

Favored by
 Metal ions with d8 configuration (Ni2+, Pd2+, Pt2+ and Au3+) mostly,
d9 (Cu2+), d7(Co2+), d4 (Cr2+) and d6 (Co3+) in some cases.
 Nonbulky strong field ligands with strong Π-bonding ability.
 [PtCl4]2-, [PdCl4]2-, [Pt(NH3)4]2+, cis and trans-[ Pt(NH3)2Cl2],
[Ni(CN)4]2-.

8
 Coordination Number 5

Square pyramidal (C4v)

VO(acac)2, XeOF4, XF5 (X = Cl, Br, I)

Trigonal bipyramidal (D3h)

Fe(CO)5, PCl5
9
Interconversion between tbp and sp (Berry psuedorotation)

Trigonal bipyramidal Square pyramidal Trigonal bipyramidal

13C NMR of Fe(CO)5 shows only one signal

10
 Coordination Number 6

Octahedral (Oh)

M(CO)6, M= Cr, Mo, W

[Co(NH3)6]3+, [CoF6]3-

11
 Coordination Number 6

Trigonal prismatic (D3h)

W(CH3)6 Re(S2C2Ph2)3

12
 Coordination Number 7

Pentagonal bipyramidal (D5h) Capped trigonal prismatic (C2v)

[ZrF7]3-, [HfF7]3- [NbF7]2-, [TaF7]2-

13
 Coordination Number 7

Capped octahedron (C3v)

[NbOF6]3-

14
 Coordination Number 8

Cubic (Oh) Square antiprismatic (D4d)

CsCl, CaF2 [XeF8]2-, [TaF8]3-, [ReF8]2-

15
 Coordination Number 8

Dodecahedron (D2d) Bicapped trigonal prismatic (C2v)

[Mo(CN)8]4- [ZrF8]4-

16
Conversion of cube to (a) square antiprism
(b) dodecahedron

17
 Coordination Number 9

Tricapped trigonal prismatic (D3h)

[ReH9]2-, [M(H2O)9]3+ (M= La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy)
18
 Coordination Number 9

Capped square antiprismatic (C4v)

Cl-bridged [{LaCl(H2O)7}2]4+

19
 Bonding in Coordination Compounds

 Valence Bond Theory

 Crystal Field Theory

Molecular Orbital Theory

20
How & Why?

21
 Valance Bond Theory

Linus Carl Pauling

(1901-1994)
Nobel prizes: 1954, 1962

• Ligand = Lewis base

• Metal = Lewis acid
• s, p and d orbitals give hybrid orbitals with specific geometries
• Number and type of M-L hybrid orbitals determines geometry
of the complex

22
Types of Hybridization in Complexes

Coordination Hybridization Geometry

Number
2 sp (s, pz) Linear
3 sp2 (s, pz, px) Trigonal Planar
4 sp3 (s, pz, px, py) Tetrahedral
dsp2/sp2d (s, px, py, dx2-y2) Square planar
5 dsp3/sp3d (s, px, py, pz, dx2-y2) Square pyramidal
dsp3/sp3d (s, px, py, pz, dz2) Trigonal bipyramidal
6 d2sp3 (dz2, dx2-y2, s, px, py, pz) Inner Orbital
Octahedral
sp3d2 (s, px, py, pz, dz2, dx2-y2) Outer Orbital
Octahedral

23
Octahedral Complex
e.g. [Cr(NH3)6]3+

24
Tetrahedral e.g. [Zn(OH)4]2-

Square Planar e.g. [Ni(CN)4]2-

25
Limitations of VB theory
• Cannot account for colour of complexes.

•Dependent on magnetic moment.

• Cannot explain formation of square planar complexes in

d8 cases.

26
Crystal Field Theory

A purely ionic model for transition metal complexes.

Ligands are considered as point charge.

Predicts the pattern of splitting of d-orbitals.

Used to rationalize spectroscopic and magnetic properties.

27
d Orbitals

28
Octahedral Field

29
30
 d Orbital Splitting

__ __ e
g
dz2 dx2-y2
0.6∆o ∆o
__ __ __ __ __
0.4∆o
Spherical field __ __ __ t
2g
dxy dxz dyz
Octahedral field
31
Tetrahedral Field

dz 2 dx2 – y2

dxy dxz dyz

32
d Orbital Splitting

33
Tetragonal Complexes

34
Square planar Complexes

35
Square planar Complexes

• Quite common for the d8 metals in

the 4th and 5th periods: Rh(I), Ir(I),
Pt(II), Pd(II) and Au(III) because of
large ligand field stabalization
energies, favoring four-coordinate
complexes.
• Rare for the 3rd period metals. Ni(II)
generally forms tetrahedral
complexes. Only with very strong
ligands such as CN-, is square planar
geometry seen with Ni(II).

36
 Orbital splitting in different geometries
C. N. Geometry dz2 dx2-y2 dxy dyz dzx
4 Tetrahedral -2.67 -2.67 1.78 1.78 1.78

4 Square Planar -4.28 12.28 2.28 -5.14 -5.14

(Ligands are
in xy plane)
5 Trigonal 7.07 -0.82 -0.82 -2.72 -2.72
Bipyramidal
5 Square 0.86 9.14 -0.86 -4.57 -4.57
Pyramidal
(Pyramid base
in xy plane)
6 Octahedral 6.00 6.00 -4.00 -4.00 -4.00

37
Orbital splitting in different geometries

38
 Factors affecting 
[V(H2O)6]2+
1a. Oxidation state of the metal ion
[Ru(H2O)6]2+ 19800 cm-1
[Ru(H2O)6]3+ 28600 cm-1
1b.Quantum number of central metal ion
[Co(NH3)6]3+ 23400 cm-1
[Rh(NH3)6]3+ 34000 cm-1
[Ir(NH3)6]3+ 41000 cm-1

2.Number of ligands and geometry [V(H2O)6]3+

sp = 1.3 o t= 4/9o
3.Nature of the ligand
I-<S2-<SCN-<Cl-<NO3-<N3-<F-<OH-<C2O42-<H2O<…..CN-<CO
39
Spectrochemical series
Increasing
Cl- < F- < H2O < NH3 < en < NO2- < CN-

Increasing

15060 cm-1 17400 cm-1 21680 cm-1 26600 cm-1

F donor < O donor < N donor < C donor 40

 Crystal Field Splitting Energy (CFSE)

• In Octahedral field, configuration is: t2gx egy

• Net energy of the configuration relative to the average
energy of the orbitals is:
= (-0.4x + 0.6y)O
O = 10 Dq

BEYOND d3
• In weak field: O  P, => t2g3eg1
• In strong field O  P, => t2g4
• P - paring energy

41
When the 4th electron is assigned it will either go into the
higher energy eg orbital at an energy cost of Do or be paired at
an energy cost of P, the pairing energy.

d4

Strong field = Weak field =

Low spin High spin
(2 unpaired) (4 unpaired)

P < Do P > Do
42
 Placing electrons in d orbitals (include ΔO & P)

d5 d6 d7

1 u.e. 5 u.e. 0 u.e. 4 u.e. 1 u.e. 3 u.e.

d8 d9 d10

2 u.e. 2 u.e. 1 u.e. 1 u.e. 0 u.e. 0 u.e.

43
 Applications of Crystal Field Theory
The origin of the color of the transition
metal compounds
E2

DE h

E1

DE = E2 – E1 = h
Ligands influence O, therefore the colour
44
The optical absorption spectrum of [Ti(H2O)6]3+

Absorbs in green yellow.

Looks purple.

45
 Color of the transition metal compounds

absorbed observed
color color

46
 Magnetic moment of transition metal complexes

• The magnetic moment  of a complex with total spin

quantum number S is:
•  = 2{S(S+1)}1/2 B (B is the Bohr magneton)
• Since each unpaired electron has a spin ½,
• S = (½)n, where n = no. of unpaired electrons
•  = {n(n+2)}1/2 B
• In d4, d5, d6, and d7 octahedral complexes, magnetic
measurements can very easily predict weak versus strong
field.
• Tetrahedral complexes - only high spin complexes result,
for t  O.

47
Magnetic moment of transition metal complexes

Ion n S /B Experimental

Calculate
d
3+
Ti 1 1/2 1.73 1.7 – 1.8
V3+ 2 1 2.83 2.7 – 2.9
Cr3+ 3 3/2 3.87 3.8
3+
Mn 4 2 4.90 4.8 – 4.9
Fe3+ 5 5/2 5.92 5.3

48
 CFSE and Ionic radii

WF
Ionic Radii of
M2+ ions of 1st row SF
transition elements

Ionic Radii of
WF
M3+ ions of 1st row
transition elements SF

49
 Stability of oxidation states

Higher CFSE compensates Higher CFSE compensates

pairing energy ionization energy
50
 Spinels
Normal spinel
AB2O4
A= Group 2 metal/transition metal in +2 state
B = Group 13 metal/transition metal in +3 state
O2 ccp array with eight Td holes and four Oh holes per unit
A in 1/8 Td sites, B in ½ Oh sites
Ex: MgAl2O4 or Mn3O4 (Special Case:Co3O4)
Inverse spinel
B[AB]O4
A in Oh sites, ½ B in Td sites, ½ B in Oh sites
Ex: NiFe2O4 = Fe[NiFe]O4
Fe3O4 = Fe(III)[Fe(II)Fe(III)]O4 51
 Site preference in Spinels

= occupancy factor (fraction of B cations in Td sites)

 range is l = 0 (normal) to 0.5 (full inverse)

A Mg2+ Mn2+ Fe2+ Co2+ Ni2+ Cu2+ Zn2+

B d0 d5 d6 d7 d8 d9 d10
Al3+ d0 0 0 0 0 0.38 0
Cr3+ d3 0 0 0 0 0 0 0
Mn3+ d4 0 0
Fe3+ d5 0.45 0.1 0.5 0.5 0.5 0.5 0
Co3+ d6 0 0

52
Site preference in Spinels

53
Limitations of CFT

 CFT considers only metal d orbitals, not s & p. Also

Π-bonding is not explained by CFT.
 Strength of ligands can not be explained. It’s not clear why
H2O is stronger ligand than OH- and NH3 than H2O.
 The ligands containing electronegative elements are not
strong field although the bonding between metal and ligand
is ionic.

54
 The Jahn-Teller Effect
If the ground electronic configuration of a non-linear complex is
orbitally degenerate, the complex will distort so as to lower the
symmetry, remove the degeneracy and achieve a lower energy.

o >> δ1 > δ2
55
Jahn-Teller distortion in Octahedral Complex

56
 Examples

238 pm

195 pm

CuBr2: 4 Br at 240pm; 2 Br at 318pm

CuF2: 4 F at 193pm; 2 F at 227pm
CrF2: 4 F at 200pm 2 F at 243pm
KCrF3: 4 F at 214pm 2 F at 200pm
[Cu(H2O)6]2+
57
 Molecular Orbital Theory
 Molecular orbital (MO) theory considers the overlap of atomic
orbitals, of matching symmetry and comparable energy, to form
molecular orbitals.
 When atomic orbital wave functions are combined, they
generate equal numbers of bonding and antibonding
molecular orbitals.
 The bonding MO is always lower in energy than the
corresponding antibonding MO.
 Electrons occupy the molecular orbitals in order of their
increasing energy in accordance with the aufbau principal.

 Bond-Order = Electrons in BMOs – Electrons in ABMOs

2 58
Molecular Orbital Theory

59
Molecular orbital approach to bonding in octahedral complexes, ML6

Combinations of atomic orbitals Molecular Orbital

4s ± 1/√6(σ1 + σ2 + σ3 + σ4 + σ5 + σ6) a1g

4px ± 1/√2 (σ1  σ2)

4py ± 1/√2 (σ3  σ4) t1u
4pz ± 1/√2 (σ5  σ6)

3dx2 - y2 ± 1/2 (σ1 + σ2  σ3  σ4) eg

3dz2 ± 1/√12 (2 σ5 + 2 σ6  σ1  σ2  σ3  σ4)

3dxy
3dxz Non-bonding in σ complex t2g
3dyz
60
Molecular orbital approach to bonding in octahedral complexes, ML6

61
 Molecular Orbital Diagram for Octahedral Complex

σ-bonding

CFT

VBT

[Co(NH3)6]3+, ΔO = 23,000 cm-1, P = 19,000 cm-1

[CoF6]3-, ΔO = 13,000 cm-1, P = 19,000 cm-1 62
 Tetrahedral Complexes and Ligand Field Theory
A. Sigma and Pi bonding

B. Results
4 s-bonding orbitals are filled by ligand electrons
a) A1 has no match with metal other than small s-orbital
b) T2 matches dxy, dxz, dyz so these orbitals are raised in energy
c) The dx2-y2 an dz2 orbitals are not involved so stay at same energy
d) Result is an inversion of the orbital sets from octahedral complexes

63
 Molecular Orbital Diagram for Tetrahedral Complex

Since the metal 4p and t2 orbitals are of the same symmetry, e → t2

transitions in Td complexes are less “d-d” than are t2g → eg transitions in Oh
complexes. They are therefore more allowed and have larger absorbtivity
64
values (e)
Ligand Field Theory and Square Planar Complexes

A. Sigma Bonding
1) Group Theory MO Description for D4h symmetry

65
 Molecular Orbital Diagram for Square Planar Complex

• Choose dz2, dx2-y2, px, py as

most likely orbitals from
metal ion
• Three d-orbitals are not
involved in s-bonding
(dxy, dxz, dyz)
• The s-bonding diagram is
complex because the d-
orbitals are split into three
different groups.
• The energy difference
between the lowest 2 d-
orbital groups is called D 66
 π Bonding in Octahedral Complex

The ligand may have empty d or π* orbitals and serve as a π

acceptor ligand, or full p or d orbitals and serve as a π donor ligand.

Type Nature Example

PΠ-dΠ L M O2-, F-, Cl-
dΠ-dΠ M L R3P, R2S
dΠ-Π* M L CO, CN-, N2,
dΠ-σ* M L H2
67
 Case 1 (CN-, CO, C2H4)
empty π-orbitals on the ligands
Π-bonding
ML π-bonding (π-back bonding) t2g (π*)

t2g

eg
eg

Do
D’o Do has increased

t2g
Stabilization

t2g (π)

ML6 ML6
(empty π-orbitals on ligands)
s-only s+π 68
 Case 2 (Cl-, F-)
filled π-orbitals on the ligands Π-bonding
LM π-bonding

eg eg
D’o
t2g (π*)
Do has decreased
Do

Destabilization

t2g

t2g

Stabilization
t2g (π)

ML6 ML6
(filled π-orbitals)
s-only s+π 69
Π-bonding

70
Molecular Orbital Diagram for [Ni(CO)4]

71
 π Bonding in Square Planar Complex
1) dxy dxz and dyz can have p-bonding

2) p-orbitals of metal too small

Complete MO Diagram
1) s-bonding set filled by L electrons
2) p-donor set
a) Filled by L electrons if present F- p-orbitals or CN- p-orbitals
b) Overall destabilizing on d-set
3) Metal d-orbitals split into 4 groups
4) d8 metals favor square planar due to large gap to high energy orbital (a2u)
72
π Bonding in Square Planar Complex

73
1. All ligands are σ donors. In general, ligands that engage
solely in σ bonding are in the middle of the spectrochemical
series. Some very strong σ donors, such as CH3- and H- are
found high in the series.

2. Ligands with filled p or d orbitals can also serve as π donors.

This results in a smaller value of ∆o.
3. Ligands with empty p, d or π* orbitals can also serve as π
acceptors. This results in a larger value of ∆o.
I-<Br-<Cl-<F-<H2O<NH3<PPh3<CO
π donor< weak π donor<σ only< π acceptor
74
 ?
 Explain why Cu+ salts are white while Cu2+ salts are blue.
For Ni2+, cyanide ion forms a square planar complex, but
ammonia and water form octahedral complex and chloride,
bromide and iodide form tetrahedral complex.
 Explain why [NiCl4]2- is tetrahedral and paramagnetic,
whereas [PtCl4]2- is square planar and diamagnetic.
 [CoF6]3- is paramagnetic (μ = 4.89 BM), whereas [NiF6]2- is
diamagnetic (μ= 0), explain.
 High spin Fe2+ has a radius of 92 pm, where low spin Fe2+
has 75 pm, explain.
75
 ?
1. The set of ions expected to show Jahn-Teller distortion
in their complexes is:
a) Ti(III), Cu(II), High spin Fe(III) b) Cu(I), Ni(II), High spin Fe(III)
c) Cu(II), Ti(III), Low spin Fe(III) d) Cu(I), Mn(II), Low spin Fe(III)

2. The number of manganese ions in tetrahedral and octahedral sites,

respectively in Mn3O4 are:
a) One Mn2+ and two Mn3+ b) One Mn3+ and two Mn2+
c) Two Mn3+ and one Mn2+ d) Two Mn2+ and one Mn3+

3. Which one of the following complex is paramagnetic?

a) [Ni(H2O)6]2+ b) [Zn(NH3)4]2+
c) [Ni(CO)4] d) [Co(NH3)6]3+

4. The complex with spin-only magnetic moment of 4.9 BM is

a) [Fe(H2O)6]2+ b) [Fe(CN)6]3-
c) [Fe(CN)6]4- d)[Fe(H2O)6]3+ 76