Rate Law for Dissociative Mechanism

1
 Rate Law for Interchange Mechanism

§ Assumptions to simplify the analysis:

1. [Y] = very large, [Y]0 = [Y]
2. k2 << k-1 which means reaction #1 is in equilibrium with K1 = k1/k-1
3. [ML5X]0 = [ML5X] + [ML5X•Y]

§ Steady State Equation:

2
Rate Law for Associative Mechanism

3
 Rate Law for Associative Mechanism

§ Derivation of Rate Law:

4
 Experimental Evidences of Intimate Mechanism

§ Acid hydrolysis (Aquation):

ML5Xn+ + H2O → ML5(H2O)(n+1)+ + X-

e. g. [Co(NH3)5X]n+

-Same entering group, but different leaving group

- Reaction rate is dependent on the leaving group

§ Anation:
ML5(H2O)(n+1)+ + Y- → ML5Yn+ + H2O

e. g. [Co(NH3)5(H2O)]3+
-Same leaving group, but different entering group
- Reaction rate is independent on the entering group

Ø These two set of experiments suggest d intimate mechanism.

Ø In case of anation of [Ti(H2O)6]3+ by different Y-, rate is dependent on
nature of Y, hence a intimate mechanism. 5
 Nature of Entering and Leaving Groups

§ Rate Constant for Aquation: Co(NH3)5Xn+ + H2O → Co(NH3)5 (H2O)(n+1)+ + X-

Complex k (s-1)
[Co(NH3)5(OP(OMe)3)]3+ 2.5 x 10-4
[Co(NH3)5(NO3)]2+ 2.4 x 10-5
Rate is dependent on the
nature of leaving group.
[Co(NH3)5(N3)]2+ 2.1 x 10-9
[Co(NH3)5(NCS)]2+ 3.7 x 10-10

§ Rate Constant for Anation: Co(NH3)5(H2O)(n+1)+ + Y- → Co(NH3)5Yn+ + H2O

Yn- k (s-1)
H2O 100 x 10-6
Rate is independent on the
N3 100 x 10-6
nature of entering group.
SO42- 24 x 10-6
Cl- 21 x 10-6

Ø d activation mechanism 6
 Steric Effects of Inert (Non-Leaving) Groups

§ Crowding around the metal decreases the rate that occur by a mechanism and
increases those occurring via d mechanism.

§ Rate Constant for Aquation:

trans-[Co(N4)LCl]n+ + H2O → trans-[Co(N4)L(H2O)](n+1)+ + Cl-
Complex k (s-1)
trans-[Co(cyclam)(NCS)Cl]+ 1.1 x 10-9
trans-[Co(tet-b)(NCS)Cl]+ 7.0 x 10-7

§ Rate increases on going from cyclam complexes to those of its hexamethyl

analogue tet-b. Steric acceleration occurs.

NH HN NH HN

NH HN NH HN

cyclam ( 1,4,8,11-tetraaza tet-b ( 1,4,8,11-tetraaza-5,5,7,12,12,14-

cyclotetradecane) hexamethylcyclotetradecane) 7
 Electronic Effects of Inert (Non-Leaving) Groups

NH3 → σ-donor Cl-, OH- → π-donor CN- → π-acceptor

§ Rate Constant for Aquation: [Co(en)2LCl]n+ + H2O → [Co(en)2L(H2O)](n+1)+ + Cl-

Complex k (s-1)
cis-[Co(en)2Cl2]+ 2.4 x 10-4
trans-[Co(en)2Cl2)]+ 3.5 x 10-5
cis-[Co(en)2(OH)Cl]+ 1.6 x 10-3
trans cis
cis-[Co(en)2(NH3)Cl]+ 5.0 x 10-7
cis-[Co(en)2(CN)Cl]+ 6.2 x 10-7 Rate constant: cis > trans

§ Rate constants for cis-[Co(en)2LCl]n+ (L = OH-, NH3, CN-):

OH- > CN- ~ NH3 Ø d activation mechanism

▪ After departure of X, if cis ligand is good π-donor, can supply electrons to electron
deficient Co, stabilizing transition state and lowering activation energy.

▪ If L is trans to X, no π-donation into vacant Co orbital can occur without

rearrangement to a trigonal bipyramid. 8
 Effect of Charge on Reaction Rate

§ Increased positive charge should make bond breaking between ligands and metal
more difficult. Hence, rate will decrease with increasing positive charge for d
mechanism.

§ Rate constants for anation by Yn- for [Fe(H2O)6]3+ and [Fe(OH)(H2O)5]2+:

Yn- k (M-1 s-1) for [Fe(OH)(H2O)5]2+ k (M-1 s-1) for [Fe(H2O)6]3+
SO42- 1.1 x 105 2.3 x 103
Cl- 5.5 x 103 4.8
Br- 2.6 x 103 1.6
NCS- 5.1 x 103 90
ClCH2CO2- 4.1 x 104 1.5 x 102
H2O 1.2 x 105 1.6 x 102

§ The rate increase for less positively charged hyroxo complexes implies a
d activation.