Coordination Compounds:

Reactions and Mechanism

Part III
TYPES OF REACTIONS
I. Substitution Reaction
Mechanism:
Ligand Substitution:
ML4 + L’ ML3 L’ + L (Td)
ML6 + L’ ML5 L’ + L (Oh)

Note: No change in Coordination Number(CN) and

Oxidation State (OS) of the central metal atom
Example:
[PtCl4 ]2- + NH3 [PtCl3 NH3 ]- + Cl-
[Cr(CO)6 ]2+ + py [Cr(CO)5 py]2+
A. Kinetic Terms

• Inert
– Exchange ligand in a very slow rate
– t1/2 > one minute at room temp
• Labile
– Exchange ligand in a very fast rate
– t1/2 < one minute at room temp
Examples:

[Co(NH3)6]3+ + 6[H3O]+  [Co(H2O)6 ]3+ + 6NH4+

- Thermodynamically unstable and kinetically
inert

[Ni(CN)4]2- + 4 CN-1  [Ni(CN)4]2- + 4 CN-1

- Thermodynamically stable and kinetically labile
Notes:
• metal ions with electron in antibonding eg
orbital, ligand substitution is not easy due to
M-L bond.
• Metal ions with electron in the bonding
orbital, ligand substitution should not be
difficult due to the absence of electrostatic
repulsion (rapid)
B. Octahedral Complexes
1. SN1 or Dissociative (D) mechanism
- normally form 5 membered complex where
large (+) Ssystem (one molecule breaking into
more molecules)
- the rate is dependent on one species
Example:
ML6  ML5 + L
ML5 + L’  ML5L’
2. SN2 or Associative (A) Mechanism
- Bimolecular Nucleophilic Substitution that
form 7 membered complex
Example:
ML6 + L’  ML6L’
ML6L’  ML5L’ + L
Net: ML6 + L’  ML5L’ + L

Rate = k [ML6+*L’+
3. Mixed type

trans-[Co(en)2Cl2]+ + H2O trans-[Co(en)2Cl(H2O)]2++ Cl-

Rate = kobs [trans-[Co(en)2Cl2]+
Where kobs = k1 + k2 [H2O]

Propose the mechanism involved in this reaction.

4. Isomerization Reaction
– Chemical reaction that involves bond breaking and
bond forming
Example:
Trans-[Co(en)2Cl2]+ cis- [Co(en)2 Cl2]+

- Intramolecular twist without bond breaking nd

bond forming
a. Bailar twist and
b. Ray-Dutt twist
C. Square Planar Complexes

– For Pt(II), sometimes for Rh(I), Ir(I), Pd(II), Au(III),

d8 or d9 -like configuration
Example:
[Pt(NH3 )4 ]2+ + Cl- [Pt(NH3 )3 Cl]+ + NH3
Rate = kobs [Pt(NH3 )4 ]2+ where
kobs = k1 + k2 [Cl-]
Trans Effect

– Labilization of ligand trans to a substituent

Order of decreasing trans-directing ability of

ligands:
CO~CN- ~ C2H4 > PR3 (R = allyl, aryl) > H- >Me-
>Ph- ~ NO2- ~ I- SCN- > Br- > Cl- >py > NH3 > F-
~ OH- > H2O
Trans Effect Theory
1. Polarization Theory
- the more polarizable the substituent, the greater the trans
directing ability ( with a substituent that is more polarizable,
the ligand directly opposite will be removed)
Polarizability: H- > Me-
I- > Br- > Cl- > F-
2. - Activation Theory
- pi bonding capable of trans directing thru pi electrons from
central metal and therefore weakens the M-L bond trans to it
- because of pi overlap, the electron density opposite to pi
overlap because lower and the position trans to the ligand will
have less electron density than in the pi bonding orbitals
D. Tetrahedral Complexes

– Fast substitution
– Involve associative mechanism
– Intermediate: 5-membered complex
Example:
[Co(CO)3(NO)] + L [Co(CO)2(NO)L] + CO
II. Redox (Oxidation-Reduction) Reaction

– Involves electron transfer

Example:
[V(H2 O)6 ]2+ + 2H+ 2 [V(H2 O)6 ]3+ + H2

What is the oxidation reaction for this?

What is the reduction reaction for this?
Ligand Transfer:

[Co(NH3 )5Cl] + [Cr(H2O)6]2+ + 3H2 O

CN = 6 OS = 3 CN = 6 OS = 2

[Co(H2O)6]2+ + [Cr(H2O)5 Cl]2+ + 5NH4+

III. Addition / Dissociation

- there is a change in coordination number but

no change in oxidation state
- it involves electron defficient center with
vacant orbitals readily forming complexes
through the addition of extra ligand.
Examples:

• Addition Reaction
BF3 + F-  [BF4 ]-
B(III) B(III)
CN : 3 CN : 4
• Dissociation Reaction
[Cr(CO)5 (Cs)]  [Cr(CO)4 (Cs)] + CO
CN : 6 CN : 5
IV. Oxidative Addition / Reductive Elimination

– There is a change both in C.N and O.S of the

central metal atom

Example:
Oxidative Addition
2[Co(CN)5 ]3- + H2 2[Co(CN)5 H]3-
Co (II) H (0) Co(III) H(-1)
CN : 5 CN : 6
Reductive Elimination
[PdCl6 ]2-  [PdCl4 ]2- + Cl2
Pd(IV) Cl(-1) Pd(II) Cl(0)
V. Free Radical

– Reaction involving paramagnetic species and

sometimes photochemically activated species
VI. Insertion Reaction

- placement of a group between central metal

atom and another ligand bonded to it without
a change in O.S and C.N
Example:
CH3 Mn(CO)5 + PPh3 CH3 COMn(CO)4 (PPh3 )

Note: CO is inserted between methyl group and Mn