Reaction and Mechanism

REACTIONS AND MECHANISMS
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.
Background
Transition-state theory
a transition state without any structures an intermediate, is formed along the

at local energy minima reaction pathway with detectable
structure.
Background
Transition-state theory
The reaction can
occur quickly due to
the low activation
energy,
Large and positive equilibrium constants since ∆G < 0;

but it has a small
both reactions are spontaneous.
equilibrium constant
∆G > 0.
Substitution Reactions
Inert and Labile Compounds
Kinetically Inert/Labile vs Thermodynamically Unstable/Stable Compounds
A labile complex has a very low Compounds that react more slowly are
activation energy for ligand substitution. called inert.
Kinetically Inert/Labile vs Thermodynamically Unstable/Stable Compounds
KR = 1030; ∆G < 0 ; in fact, the rate of reaction is too slow

→ [Co(NH3)6]3+ is thermodynamically unstable, but kinetically inert.
[Ni(CN)4]2- + H2O → no any reactions

→ [Ni(CN)4]2- is thermodynamically stable, but kinetically labile.
Dissociation D Association (A)
Interchange (I)
Dissociation D
Association (A) d [ ML5 XY ]

 k1[ ML5 X ][Y ]  k1[ ML5 XY ]  k2 [ ML5 XY ]  0
dt
k [ ML5 X ][Y ]
 [ ML5 X ]  1
k1  k2
d [ ML5Y ] k k [ ML5 X ][Y ]
r  k2 [ ML5 XY ]  1 2  kobs [ ML5 X ][Y ]
dt k1  k2
Interchange (I)
M-Y > M-X: Ia mechanism.

M-Y < M-X: Id mechanism
Preassociation Complex
Experimental Evidence in Octahedral Substitution
Dissociation
Dissociation
The ligand field activation energy (LFAE), defined as the difference between the
LFSE of the square-pyramidal transition state and the LFSE of the octahedral reactant
Dissociation
1. Oxidation state of the central ion: Central atoms with higher oxidation states
have slower ligand exchange rates.
2. Ionic radius. Smaller ions have slower exchange rates.

Linear Free-Energy Relationships
CFSE (+), the rate(-)

Stable bond (+), the rate(-)
The Kinetic Chelate Effect
The ∆H associated with

removal of the first bound
atom is larger than for
subsequent reattachment .
The rate constants do not vary significantly

with the substituting anion Y, as would be
expected for a D or Id mechanism
Association
Ia and A reactions are less common with octahedral complexes due to steric hindrance.
The rates depend on significantly nature of incoming ligands.
Substitution Reactions of Square-Planar Complexes
Solvent-assisted substitution
rate determining step,

Rate constant = kY
rate determining step,

Rate constant = kS
A or Ia mechanism
The rates of reactions depend on nature of incoming L  A mechanism

- The rate depends on significantly L.

- The rate of incoming L.
- The rate of leaving X.

KY path way – A or Ia - geometry preservation
KS path way – geometry preservation
The trans effect
The trans effect: A ligand affects an other ligand placed in trans position,
which trans-placed ligand is more flexible to leave for substitution reaction.
The trans effect
The trans effect does not

always determine product.
The trans effect
The explanation of trans effect - the trans influence
Sigma-Bonding Effects
Poor trans effect: σ Bonding effect: π Bonding effect:

low ground state, higher ground state lower transition state,
high transition state (trans influence) (trans effect)
The Pt-T bond is strong, it uses a larger contribution of

px, dx2-y2 orbitals of Pt atoms  the Pt-X bond is
weaker,  its ground state (sigma-bonding orbital) is
higher in energy .
The trans influence on the basis of the relative σ donor properties of the ligands:
Pi-Bonding Effects
A strong π-acceptor Pt-T charge is removed from Pt
metal center more electrophilic and more susceptible to nucleophilic attack.
 formation of the 5-coordinate intermediate with a relatively strong Pt—Y
bond, stabilizing the intermediate by increase in energy due to the M—X bond
breaking.
 The energy of the transition state is lowered, reducing the activation energy.
Oxidation–Reduction Reactions
Inner-sphere vs Outer-sphere reaction
Inner-sphere reaction Outer-sphere reaction

The electron exchange may occur
Electrons transfer through bridging between two separate coordination
ligand. spheres.
Bridge ligand must have 2 pairs of

electrons at least. Ligand is unable to bridge anothers.
Inner-sphere reaction
Inner-sphere Henry-Taube reaction (Nobel 1983)
Inner-sphere reaction
Which is the determining step in

case of a, b and c?
Outer-sphere reaction
1. Sox – Sred = +/-1/2
2. For octahedral
complexes, an electron
is transferred on t2g
orbitals.
3. No change in
geometry of reactant,
product molecules.
Reactions of Coordinated Ligands
Hydrolysis of Esters, Amides, and Peptides
Reactions of Coordinated Ligands
Template Reactions
Problem 1
1.1. The high-spin d4 complex [Cr(H2O)6]2 + is labile, but the low-spin d4 complex
ion [Cr(CN)6]4 - is inert. Explain.
1.2. Data for the reaction
Co(NO)(CO)3 + As(C6H5)3 → Co(NO)(CO)2[As(C6H5)3] + CO
in toluene at 45 °C are given in the table. In all cases, the reaction is pseudo–first
order in Co(NO)(CO)3.
Determine the rate constant(s) and discuss their probable significance (See E. M.
Thorsteinson, F. Basolo, J. Am.Chem. Soc., 1966, 88, 3929).
Problem 2
2.1. The CO exchange reaction
Cr(12CO)6 + 13CO → Cr(12CO)5(13CO) + 12CO
has a rate that is first order in the concentration of Cr(12CO)6 but independent of
the concentration of 13CO. What does this imply about the mechanism of this
reaction?
2.2. The reaction Cr(CO)6 + PR3 → Cr(CO)5PR3 + CO [R = P(n-C4H9)3] has the

rate law of rate = k1[Cr(CO)6] + k2[Cr(CO)6][PR3].
Why does this rate law have two terms?
2.3. For the general reaction in part 2.2, will bulkier ligands tend to favor the first
order or second order pathway?
Explain briefly.
Problem 3
3.1. Predict the products (equimolar mixtures of reactants):
3.2. Design a sequence of reactions, beginning with [PtCl4]2 -, that will result in
Pt(II) complexes with four different ligands—py, NH3, NO2-, and CH3NH2
—with two different sets of trans ligands. (CH3NH2 is similar to NH3 in its trans
effect.)
3.3. Pt(II) can be oxidized to Pt(IV) by Cl2 with no change in configuration (chloride
ions are added above and below the plane of the Pt(II) complex). Predict the
results if the two compounds from (a) are reacted with Cl2 and then with 1 mole of
Br - for each mole of the Pt compound.
Problem 4
4.1. Is the reaction [Co(NH3)6]3 + + [Cr(H2O)6]2 + likely to proceed by an inner-

sphere or outer-sphere mechanism? Explain your answer.
4.2. The rate constant for electron exchange between V2 +(aq) and V3 +(aq) is
observed to depend on the hydrogen ion concentration:
k = a + b / [H +]
Propose a mechanism, and express a and b in terms of the rate constants of the
mechanism.
(Hint: V3 +(aq) hydrolyzes more easily than V2 +(aq).)
Problem 5
cis-PtCl2(PEt3)2 is stable in benzene solution. However, small amounts of free

triethylphosphine catalyze establishment of an equilibrium with the trans isomer:
cis-PtCl2(PEt3)2 ↔ trans-PtCl2(PEt3)2
For the conversion of cis to trans in benzene at 25 °C, ∆Ho= 10.3 kJ mol -1 and
∆So= 55.6 J mol - 1 K - 1.
a. Calculate the free energy change, ∆Go, and the equilibrium constant for this
isomerization.
b. Which isomer has the higher bond energy? Is this answer consistent with what
you would expect on the basis of pi bonding in the two isomers? Explain briefly.
c. Why is free triethylphosphine necessary to catalyze the isomerization?

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REACTIONS AND MECHANISMS

TRAN BUU DANG

a transition state without any structures an intermediate, is formed along the

Large and positive equilibrium constants since ∆G < 0;

KR = 1030; ∆G < 0 ; in fact, the rate of reaction is too slow

[Ni(CN)4]2- + H2O → no any reactions

Association (A) d [ ML5 XY ]

M-Y > M-X: Ia mechanism.

2. Ionic radius. Smaller ions have slower exchange rates.

CFSE (+), the rate(-)

The ∆H associated with

The rate constants do not vary significantly

rate determining step,

rate determining step,

The rates of reactions depend on nature of incoming L  A mechanism

- The rate depends on significantly L.

- The rate of leaving X.

The trans effect does not

Poor trans effect: σ Bonding effect: π Bonding effect:

The Pt-T bond is strong, it uses a larger contribution of

Inner-sphere reaction Outer-sphere reaction

Bridge ligand must have 2 pairs of

Which is the determining step in

1. Sox – Sred = +/-1/2

2.2. The reaction Cr(CO)6 + PR3 → Cr(CO)5PR3 + CO [R = P(n-C4H9)3] has the

4.1. Is the reaction [Co(NH3)6]3 + + [Cr(H2O)6]2 + likely to proceed by an inner-

cis-PtCl2(PEt3)2 is stable in benzene solution. However, small amounts of free

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