Consecutive Stability Constants in Solution

! In aqueous solution, formation of a complex generally proceeds by

steps involving displacement of water molecules in the first hydration
sphere.

! Equilibrium constants K1, K2, ..., Kn associated with addition of each

ligand are called consecutive stability constants.

[Cu(H2O)6]2+ + NH3 º [Cu(NH3)(H2O)5]2+ + H2O K1 = 2 x 10+4

[Cu(NH3)(H2O)5]2+ + NH3 º [Cu(NH3)2(H2O)4]2+ + H2O K2 = 4 x 10+3
[Cu(NH3)2(H2O)4]2+ + NH3 º [Cu(NH3)3(H2O)3]2+ + H2O K3 = 1 x 10+3
[Cu(NH3)3(H2O)3]2+ + NH3 º [Cu(NH3)4(H2O)2]2+ + H2O K4 = 2 x 10+2

! Successive stability constants decline through the series, such that K1 >
K2 > ... > Kn.
• In the first step there are six sites for NH3 substitution, but in the
reverse step there is only one site for H2O substitution; K1 % 6/1 .
• In the second step there are five sites for NH3 substitution, but in the
reverse step there are two sites for H2O substitution; K2 % 5/2.
• By similar reasoning we predict K3 % 4/3 and K4 % 3/4.

Ratio Predicted Observed

K1/K2 (6/1)/(5/2) = 2.40 5
K2/K3 (5/2)/(4/3) = 1.87 4
K3/K4 (4/3)/(3/4) = 1.78 5

L Agreement between predicted and observed ratios is remarkably

good, considering that predictions are based only on statistical
factors.
T Statistical factors appear to be the main cause of the trend.
 Cumulative Stability Constant

! The product of consecutive stability constants is the cumulative stability

constant, βn.

• When the overall equilibrium lies to the right the product complex is
said to be stable.
• When the overall equilibrium lies to the left the product complex is
said to be unstable.

Example: [Cu(H2O)6]2+ + 4NH3 º [Cu(NH3)4(H2O)2]2+ + 4H2O

β4 = (2 x 10+4)(4 x 10+3)(1 x 10+3)(2 x 10+2) = 1.6 x 10+16

K [Cu(NH3)4(H2O)2]2+ is a very stable complex.

 Stable/Unstable and Labile/Inert

! "Stable" and "unstable" refer to the thermodynamics of complex

formation (e.g., K, β).

! "Labile" and "inert" refer to the kinetics of complex formation.

! A complex whose formation equilibria are established rapidly is labile.

! A complex whose formation equilibria are established slowly is inert.

Example: [Cu(NH3)4(H2O)2]2+ has a large β4 and its equilibria are

established rapidly; therefore, the complex is stable and labile.

L As a "rule of thumb", if the half-life of a complex in a substitution

reaction is less than one minute, it is labile.1

1
H. Taube, Chem. Rev., 1952, 50, 69.
 Stability Constants and Thermodynamic State Functions

! The stability constant for a complex is related to ΔG, ΔH, and ΔS of its
formation by
ΔG = –RT lnβn = ΔH – TΔS

! The larger βn is, the more negative (favorable) ΔG will be.

! Entropy plays an important role.

• The more positive ΔS is, the more negative ΔG will be, and the
greater βn will be.
• Entropy is largely responsible for the greater stability constants
observed for chelates, compared to complexes of unidentate ligands
with the same metal ion.
 Chelate Effect - Entropy Factors

! The chelate effect is the name given to the general observation that
chelate complexes have higher stability constants compared to similar
unidentate ligand complexes.

Example: [Cd(NH2CH3)4]2+ vs. [Cd(en)2]2+

[Cd(H2O)6]2+ + 4NH2CH3 º [Cd(H2O)2(NH2CH3)4]2+ + 4H2O logβ4 = 6.6

[Cd(H2O)6]2+ + 2en º [Cd(H2O)2(en)2]2+ + 4H2O logβ2 = 10.6

T For both, ΔH should be about the same, because the enthalpy change
is due mainly to the change in bond strengths between Cd–O and
Cd–N, so the difference in β values must be due principally to
entropy differences.
T For [Cd(NH2CH3)4]2+, the reaction equation has equal numbers of
particles on both sides (5), so ΔS . 0.
T For [Cd(en)2]2+, there are three (3) particles on the left and five (5) on
the right, so ΔS > 0.
T The greater positive entropy change for formation of the chelate
complex results in a more negative ΔG and a larger β value.

K In general, chelates have an entropy advantage over similar

unidentate ligands.
 Chelate Effect - Kinetic Factors

! We can make a mechanistic argument for the chelate effect by

comparing the following idealized mechanisms and the associated rate
constants for each step.
ka
T Unidentate case: M+L ML
kb
kc
ML + L ML2
kd
k'a
T Chelate case: M + L—L M—L—L
k'b

k'c L
M—L—L
k'd
M
L
T For the first step in each case we can predict ka . k'a and kb . k'b.

T But for the second steps

kc < k'c random vs. directed second substitution
kd $ k'd chelate bond breaking same or harder

T Stability constants are defined in terms of the rate constants as

T From the relationships among the k values, βuni < βchel.

K In general, chelates have a kinetic advantage over comparable

unidentate ligands.
 Labile vs. Inert

! Stable/unstable are thermodynamic terms, and labile/inert are kinetic

terms, which can be applied in all possible combinations to various
complexes.

T [Co(NH3)6]3+ is unstable with respect to aquation but inert.

slow
3+ +
[Co(NH3)6] + 6H3O [Co(H2O)6]3+ + 6NH4+ K . 10+25

T [Ni(CN)4]2– is stable with respect to exchange with labeled CN– but

labile because the equilibrium is established quickly.
fast
2– –
[Ni(CN)4] + CN* [Ni(CN)3CN*]2– + CN– K . 10–22

! Most first-row transition metal complexes are labile, but

Cr3+ (d 3, S = 3/2) and low-spin Co3+ (d 6, S = 0) are usually inert.

! Inert octahedral complexes tend to be those with highest CFSE; viz., d 3,

low-spin d 4– d 6.
• ML6 complexes of both d 3 (4A2g) and low-spin d 6 (1A1g) are immune
from Jahn-Teller distortions and therefore can be perfect Oh.
• ML6 d 3 has CFSE = –(6/5)Δo and low-spin d 6 has CFSE = –(12/5)Δo
+ 3P.

! d 7– d 10, with filling of eg* levels, are labile.

• These configurations tend to have large Jahn-Teller distortions and/or
low CFSEs.
• d 7, d 9, and d 10 cases are more labile than d 8.
• d 8 has a 3A2g ground state, which is immune to Jahn-Teller distortion.
• With strong-field ligands, d 8 may be square planar, often being inert.
 Substitution Mechanisms

! Ligand substitutions follow the general stoichiometry

ML5X + Y º ML5Y + X

! Kinetic studies of the rates of such reactions provide data that suggest
the detailed mechanisms by which substitution occurs.

! Two extreme models can be postulated:

Î dissociation (D)
Ï association (A).
 Dissociation Mechanism (D) – SN1
k1
ML5X ML5 + X fast
k-1
k2
ML5 + Y ML5Y slow

Rate = k2[ML5][Y]

! The rate-determining step involves addition of Y to a CN5 intermediate

formed by a rapid equilibrium in the first step.

! Assuming a steady state in [ML5], we can write

= 0 = k1[ML5X] – k–1[ML5][X] – k2[ML5][Y]

! Solving for [ML5], we have

! Substituting into Rate = k2[ML5][Y] gives

! If product formation is fast (k2 >> k–1), or if the system has very large
[Y] (>>[X]), then rate becomes first-order in [ML5X]; i.e.,

Rate . k1[ML5X]

! Thus, the SN1 mechanism is first-order in [ML5X].

 Association Mechanism (A) – SN2

k1
ML5X + Y ML5XY fast
k-1
k2
ML5XY ML5Y + X slow

Rate = k2[ML5XY]

! Applying a steady-state approximation for [ML5XY] we have

= 0 = k1[ML5X][Y] – k–1[ML5XY] – k2[ML5XY]

! Solving for [ML5XY] we obtain

! Substituting into Rate = k2[ML5XY] gives

where k = k1k2/(k–1 + k2).

! Thus, the SN2 mechanism is second-order overall; i.e., first-order in

[ML5X] and first-order in [Y].
 Interchange Mechanism (I)

! It is too simplistic to assume that a first-order rate law implies D (SN1)

and a second-order rate law implies A (SN2).
• Most substitution reactions probably involve a mechanism that is
intermediate between these extremes, a mechanism called
interchange (I).

! In an interchange mechanism the intermediate involves an association

between the original ML5X complex and the attacking Y ligand.
• The Y ligand remains outside the coordination sphere of ML5X,
unlike the SN2 mechanism, so the intermediate is not seven
coordinate.
L
L L
M Y
X L
L

k1
ML5X + Y ML5X•Y fast
k-1
k2
ML5X•Y ML5Y + X slow

! It can be shown2 that the rate is given by

where [ML5X]o and [Y]o are initial concentrations.

• At high [Y], [Y] . [Y]o and k1N[Y]o >> 1, and the rate is first-order in
[ML5X].
• At lower [Y] the rate is second order.

2
Miessler & Tarr, 3rd ed., p. 418.
 Variations on I

! Two minor variations on the I mechanism are Id (dissociative

interchange) and Ia (associative interchange) interchange.

! If breaking the M–X bond is more important, the mechanism is Id.

! If bond formation between ML5X and Y is significant, the mechanism is

Ia.

! Difference between Id and Ia is subtle and does not necessarily

correspond to whether the observed rate law is first or second order.
 Substitution Reactions in Solvent Water

! Many substitution reactions occurring in solvent water may have first-

order kinetics regardless of whether their initial steps are primarily D or
A.
• For example, this occurs if aquation is a precursor rate determining
step.
D or A
ML5X + H2O ML5(H2O) + X slow
ML5(H2O) + Y ÷ ML5Y + H2O fast

• If D, Rate = k[ML5X].

• If A, Rate = k[ML5X][H2O], but with solvent water [H2O] is constant

and Rate = kN[ML5X].

L Both mechanisms lead to apparent first-order kinetics in solvent

water.
 Factors Favoring D or Id

! For most octahedral complexes, steric factors inhibit formation of a

CN7 intermediate, which suggests a dissociative mechanism (D or Id) is
more plausible.
• Even cases showing second-order kinetics may not be A for this
reason.

! For example, aquation of the ammine-halide complexes [Co(NH3)5X]2+

is second order with a first-order dependence in [OH–].
• Although this might suggest A, that appears unlikely.

[Co(NH3)5X]2+ + H2O ÷ [Co(NH3)5(H2O)]3+ + X–

Rate = k1 [Co(NH3)5X2+] + k2 [Co(NH3)5X2+][OH–]

• If k2 >> k1 the rate is approximately Rate . k2 [Co(NH3)5X]2+[OH–].

• From the second-order kinetics, this appears to be A, but it is more

likely an alternative mechanism called SN1CB, where "CB" stands for
"conjugate base."
 SN1CB Mechanism

! The postulated SN1CB mechanism involves the following steps:

K
2+ –
[Co(NH3)5X] + OH [Co(NH3)4(NH2)X]+ + H2O
D
[Co(NH3)4(NH2)X]+ slow
[Co(NH3)4(NH2)]2+ + X–
[Co(NH3)4(NH2)]2+ + H2O fast [Co(NH3)4(OH)]2+ + NH3
[Co(NH3)4(OH)]2+ + H+ fast [Co(NH3)5(H2O)]3+

! The second step, which is rate determining, is D (SN1), for which

Rate = k [Co(NH3)4(NH2)X+]
• But

(No [H2O] because water is solvent.)

• Solving K gives
[Co(NH3)4(NH2)X+] = K [Co(NH3)5X2+][OH–]
• Substituting into the expression for Rate gives
Rate = kK [Co(NH3)5X2+][OH–]

L This is the same as the observed rate

Rate = k1 [Co(NH3)5X2+] + k2 [Co(NH3)5X2+][OH–]
when k2 >> k1; i.e.,
Rate = k2 [Co(NH3)5X2+][OH–]

! Although steric factors favor D-type mechanisms for octahedral

complexes, square planar ML4 complexes are not so inhibited.
• For square planar ML4 complexes, an associative (A) mechanism, in
which a CN5 intermediate is formed, is plausible.
 Trans Effect

! Substitution of square planar complexes, such as PtLX3, leads to a

mixture of trans and cis isomers.

X
L Pt Y
X
X
L Pt X + Y- + X-
X
X
L Pt X
Y
! The rate law is
Rate = k1[PtLX3] + k2[PtLX3][Y–] k2 > k1

• Suggests two paths, where the first term may be pseudo-first-order

due to excess solvent acting as an attacking group.

! The ratio of trans and cis isomers is found to vary with the ability of L
to act as a trans-directing ligand.

! The increasing order of trans-directing ability is

H2O < OH– < py . NH3 < Cl– < Br– < I– < NO2– < PR3 . SH2
<< CO . C2H4 . CN–

! The effect is kinetic rather than thermodynamic.

! Two factors are cited to explain the effect:

Î Weakening of the Pt–X bond trans to the directing ligand;
Ï Stabilization of the presumed CN5 intermediate.
 M-X Bond Weakening

! For ligands at the left of the series, weakening of the trans Pt–X bond
may be most important.

! The trans-directing ligand polarizes the metal ion, inducing a slight

repulsion for the leaving ligand in the trans position.
X

L  + Pt     X  +

X
weakened by induced repulsion

! The more polarizable the L ligand, the better trans-director it is; e.g.,
I– > Br– > Cl–.
 π-Acceptor Ligands

! The strongest trans-directors are good π-acceptor ligands; e.g., CO,

C2H4, CN–.

! Assuming an A (SN2) mechanism, substitution involves a trigonal

bipyramidal transition state.

! The trans intermediate (activated complex) is more favorable for π-

acceptor ligands, because it permits π-delocalization in the trigonal
plane.
• Stabilizing the reaction intermediate lowers the activation energy, Ea,
for the reaction.
• In the cis intermediate, L lies above the trigonal plane, which
decreases its ability to stabilize the activated complex through π
delocalization.

X X
trans X
L Pt X + Y- L Pt
Y
X cis X
Y X
L Pt X
X
 Synthetic Use of the Trans Effect

! The synthetic utility of the trans effect can be illustrated by the selective
production of cis or trans Pt(NH3)2Cl2, using the greater trans-directing
ability of Cl– relative to NH3.

T To make cis-Pt(NH3)2Cl2, start with [PtCl4]2–:

Cl Cl NH3
Cl Pt Cl NH3 Cl Pt NH3 NH3 Cl Pt NH3
Cl Cl Cl
L In the second step, the greater trans-directing ability of Cl– causes
preferential substitution of NH3 in the trans position to one of the
existing Cl– ligands, resulting in the cis isomer.

T To make trans-Pt(NH3)2Cl2, start with [Pt(NH3)4]2+:

NH3 NH3 NH3
- -
H3N Pt NH3 Cl H3N Pt Cl Cl Cl Pt Cl
NH3 NH3 NH3

L In the second step, the greater trans-directing ability of Cl– causes

preferential substitution of Cl– in the trans position to the first Cl–,
resulting in the trans isomer.
 Electron Transfer Reactions
Outer Sphere Mechanism

! Transition-metal complexes can engage in redox reactions with one

another, primarily by one of two mechanisms: outer-sphere and inner-
sphere.

! In an outer-sphere reaction the coordination spheres of the reacting

complexes remain intact.
• Outer-sphere reactions are extremely fast.
• Redox occurs before ligand substitution can take place.

Example: [FeII(CN)6]4– + [IrIVCl6]2– ÷ [FeIII(CN)6]3– + [IrIIICl6]3–

inert inert

! As the charge on the metal increases, the M–L bond distance decreases.
• The effect is most pronounced when electrons are removed from an
eg* MO; e.g.,
Co2+ (t2g5eg2) ÷ Co3+ (t2g6) + e–
high-spin low-spin
long M–L shorter M–L

• Electron loss from eg* stabilizes the complex.

L The outer-sphere mechanism is certain to be the correct one when

both species participating in the reaction undergo ligand-exchange
reactions more slowly than they participate in the electron transfer
process.3

3
F. A. Cotton, G. Wilkinson, Advanced Inorganic Chemistry, 4th ed., Wiley, NY, 1980, p.
1206.
 Electron Transfer Reactions
Inner Sphere Mechanism

! Inner-sphere mechanisms generally proceed in three steps:

Î Substitution resulting in two complexes being linked through a

bridging ligand.

Ï Electron transfer, sometimes with ligand transfer.

Ð Separation of products.

! This is sometimes called a ligand-bridged mechanism, because of the

formation of the bridged intermediate.

K Inner-sphere mechanism requires that one of the participating species

have a ligand capable of functioning as a bridge.
• For example, H2O and NH3 cannot function as bridging ligands,
but Cl– and CN– can.

! Inner-sphere redox is slower than outer-sphere.

 Example of Inner Sphere Redox
+
H /H2O
[CrII(H2O)6]2+ + [CoIII(NH3)5Cl]2+ +
NH4

d4 high spin (labile) d6 low spin (inert)

[CrIII(H2O)5Cl]2+ + [CoII(H2O)6]2+
d3 (inert) d7 high spin (labile)

Mechanism:

[CrII(H2O)6]2+ + [CoIII(NH3)5Cl]2+ ÷ [(H2O)5CrII@@@Cl@@@CoIII(NH3)5]4+ + H2O

e– transfer

[(H2O)5CrIII@@@Cl@@@CoII(NH3)5]4+

[(H2O)5CrIII@@@Cl@@@CoII(NH3)5]4+ + H2O ÷ [CrIII(H2O)5Cl]2+ + [CoII(NH3)5(H2O)]2+

Co(II) complexes are labile, so [CoII(NH3)5(H2O)]2+ undergoes rapid aquation:

[CoII(NH3)5(H2O)]2+ + 5H2O ÷ [CoII(H2O)6]2+ + 5NH3

T This reaction cannot be explained as an outer-sphere mechanism

followed by Cl– substitution, because adding labeled Cl*– to the
solution yields no labeled product.
• This is expected, because all Cr(III) complexes are inert to
substitution.