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Pilkington
Variations in reactivity
Reaction types substitution, dissociation, addition and redox
reactions, reactions of coordinated ligands.
Equilibrium constants for substitution reactions.
Kinetic vs. thermodynamic stability of metal complexes
M s in rates
Measuring t s of
f water
t exchange
x h n in aquometal
m t l iions.
ns
1. Variations in Reactivity:
Let's take as a single example the difference in ligand substitution rates for
the complexes [Co(NH3)6]3+ and [Ni(NH3)6]2+ . Each complex has a negative
enthalpy for the following reaction, so both complexes are thermodynamically
capable of undergoing ligand exchange with water.
However, the exchange reaction for the nickel complex is very fast, while the
reaction for the cobalt complex takes days or weeks to go to completion. Why
is this?
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The short answer is found if we consider the reaction mechanism, i.e., how the
reaction must take place. There are two limiting possibilities, both of them
involving a 2-step reaction as shown below.
Mechanism 1. One of the NH3 ligands dissociates from the complex to give a 5-
coordinate
coord nate intermediate.
ntermed ate. This
h s intermediate
ntermed ate then forms a complex w
with
th a water
molecule.
[[M(NH
( 3)6H2O]
]n+ ---> [[M(NH
( 3)5H2O]
]n+ + NH3
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For most other ions, there is less loss (or even a gain) in CFSE on going from 6-
to 5- or 7-coordinate intermediates. Thus exchange reactions for these ions are
not retarded by the loss in CFSE.
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3. Addition Reactions increases the coordination number of the
metal. e.g.
Cu(acac)2 + py Cu(acac)2py
4-coordinate 5-coordinate
A square planar bis(acetylacetonato)copper(II) molecule accepts
a pyridine (py) ligand to form a square pyramidal product.
O O
N
Acac
Py
O O
Cr + 3Br2 Cr Br + 3HBr
O 3 O 3
Acac
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3. Equilibrium Constants for Metal Complex Formation
K1
[Ni(H2O)6]2+ [Ni(H2O)5NH3]2+ + H2O
NH3
K2
[Ni(H2O)5NH3]2+ [Ni(H2O)4(NH3)2]2+ + H2O
NH3
K6
[Ni(H2O)(NH3)5]2+ + NH3 [Ni(NH3)6]2+ + H2O
K1 = [Ni(H2O)5NH3]22+
[Ni(H2O)6]2+[NH3]
K2 = [Ni(H2O)4(NH3)2]2+
[Ni(H2O)5(NH3)]2+[NH3]
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If we only want the reaction with addition of 2NH3
Overall Reaction
Overall Constant
2+
= [Ni(H2O)4(NH3)2]
[Ni(H2O)6]2+[NH3]2
the formation
constant = beta
We can also arrive at the previous result by multiplying the first and
second equilibrium (formation) constants:
K1 x K2 = [Ni(H2O)5NH3]2+ [Ni(H2O)4(NH3)2]2+
[Ni(H2O)6]2+[NH3] ( 2O))5((NH3)]2+[[NH3]
[[Ni(H
[Ni(H2O)4(NH3)2]2+
[Ni(H2O)6]2+[NH3]2
=
6
So can we make this compound .?
[Ni(NH3)6]2+ - to decide we have to look at the formation constant.
[Ni(NH3)6]2+
6 =
[Ni(H2O)6]2+[NH3]6
= K1 x K2 x K3 x K4 x K5 x K6
i.e the formation constant is very large which means the complex
will be formed
1. Thermodynamic stability: G = H TS
where, H = enthalpy or heat change; T is the
absolute temperature, and S is the entropy
change/disorder.
G = - RTlnK
where K is the formation constant
For thermodynamic stability the requirements are K > 1, G < O this means that
the products are more stable than the reactants.
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2. Kinetic Stability refers to the rate of reaction.
Metal complexes that undergo substitution reactions very slowly are
said to be INERT.
Examples:
The equilibrium constant K for the reaction is very large and the above
reaction is instantaneous.
Hence [Co(NH3)]2+ is kinetically Labile and Thermodynamically
Unstable.
At the same time the complex anion is labile, that is the cyanide ligands
in the coordination sphere
p exchange
g rapidly
p y with those found
f free
f in
aqueous solution.
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Some coordination compounds are kinetically inert, whereas others turn
out to be labile.
Complexes of the first row transition metal ions with the exception of
Cr3+ and Co3+ are generally labile, whereas most second and third row
transition metal ions are inert.
In the case of H2O exchange you can experimentally label with 17O or
18O and you can then see which ions are kinetically labile
Ca H ion-dipole interactions.
O
Lewis acid-base if Ca2+ is assumed to
O H coordinate to the H2O
H
H
Ca2+ H
O
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Rate constants for water exchange for various ions
[M(H2O)n]x+ + 18OH
2
[M(H2O)n-118(OH2)]x+ + H2O
Very slow Very Fast
K > 10-3 to 10-6 sec-1 K > 108 sec-1
Group 1A as we go down the group the cations are getting larger and the charge
density decreases so the Mn+-OH2 bond is getting weaker and more easily broken
Group 2A the charge density is larger (doubly charged) so the strength of the
bond is greater so the rate of exchange is slower
Class 1 Groups IA, IIA and IIB as well as Cu2+ and Cr2+; k >
108. Diffusion controlled reactions
Rates of Exchange:g
Li+< Na+< K+< Cs+ Group 1A
Be2+< Mg2+< Ca 2+< Sr2+< Ba2+ Group 2A
In these two series, the smallest ions exchange the slowest:
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Li+ O2- Cs+ O2-
Coloumbs Law
E = Q+,Q-/r
d d
if we measure the distance between the centres of the atoms as used
in Coloumb's Law then we have much greater distance for Cs+-OH2.
This means the Li-OH2 bond is stronger than the Cs-OH2 since the
Lithium ion holds onto the electrons of the O2- and does not want to
break to release H2O as easily as Cs-OH2
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Classes 2 and 3 - Includes most of the first row TM ions and the
These elements who tend to undergo water exchange and ligand exchange
reactions.
For T.M. metal ions the correlation of rate with size is not obeyed, e.g. Cr2+, Ni2+,
Mn2+ > Fe2+ > Co2+ substitution rates decrease across the series. This is
Class 4 - Rate constants are in the range 10-3-10-6 sec-1. This includes
For these metal ions the rate of exchange is partially related to the size of the
cations and p
partly
y to the CFSE.
The basic assumption is that the significant contribution to the activation energy
d3 and d6 ions are predicted to be inert e.g. Rh3+, Cr3+ and Co2+
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