N K Agnihotri Chem(H) IV Seme (DSC-10) MLNC
LABILE AND INERT COORDINATION COMPOUNDS
To classify the varying rates of reaction (most commonly about substitution) of
coordination compounds, Henry Taube, who received the 1983 Nobel Prize in
chemistry for his work in the kinetics of coordination compounds, suggested the
terms labile and inert. If we consider a 0.1 M aqueous solution, a labile coordination
compound is one that under these circumstances has a half-life of less than a
minute. (Recall that half-life is the amount of time required for the concentration of
the reactant to decrease to half its initial concentration.) An inert coordination
compound, on the other hand, is one with a half-life greater than a minute.
The terms labile and inert are kinetic terms, that refer to the rate of a reaction that
in turn, is governed by its energy of activation. These terms relate to how rapidly a
compound reacts rather than to how stable it is. Stable and unstable are
thermodynamic terms. They are related to the changes in free energy, enthalpy, and
entropy of reactions involving the compound. Reactions with a large negative
change in free energy and a correspondingly large positive equilibrium constant go
spontaneously from left to right; the products of such reactions are considered
more stable than the reactants. The change in free energy can in turn be related to
the changes in enthalpy and entropy ( ΔG = ΔH - TΔS).
As far as complexes in solutions are concerned, there are two kinds of stabilities –
Thermodynamic stability and Kinetic Stability.
Thermodynamic stability – Measure of the extent to which the complex will be
formed or will be transformed into another species when the system has reached
equilibrium, i.e., the Complex is stable or unstable.
Kinetic stability – refers to the speed with which the transformations leading to
equilibrium will occur. Under this, the rates of substitutions, racemisations and their
mechanisms. Complexes are known to be labile or inert. The complexes that rapidly
exchange their ligands with other species are called labile. If the ligand exchange
reaction rate is slow, then they are called inert complexes.
But the reactive nature (Kinetic stability) should not be confused with the
stability(Thermodynamic stability). The terms labile and inert refer to the reactivity
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N K Agnihotri Chem(H) IV Seme (DSC-10) MLNC
of a complex only. It should not to be confused with its thermodynamic stability. An
inert complex may be stable or unstable. Similarly, a labile complex may be stable
or unstable. The above fact is clearly shown by the complex [Hg(CN)4]2-
Hg2+ + 4CN- [Hg(CN)4]2- β ≈ 1042
The overall formation constant is having very high value, which means that
equilibrium is lying far too right. But when this complex exchanges its CN - ligands
with 14C labeled CN- solution very high rate shows, that the complex is labile. So, the
thermodynamic stability is not connected to the lability or inertness of a complex.
The difference between kinetic lability and thermodynamic stability, we consider
some specific examples. Take the familiar Werner complex cation
hexaamminecobalt(III), [Co(NH3)6]3+; it reacts spontaneously with acid. The
equilibrium constant for the reaction is very large, in the vicinity of 1030.
Therefore, we would say that this cation is unstable toward reaction with acid. On
the other hand, it takes several days at room temperature to get this reaction to go
significantly from left to right, even in 6 M HCl. Accordingly, the rate of this reaction
is so slow that [Co(NH3)6]3+ must be classified as inert under these circumstances.
This complex cation, then, is unstable (thermodynamically) but inert (kinetically)
toward reaction with acid.
In contrast, tetracyanonickelate(II), [Ni(CN)4]2-, is exceptionally stable
(thermodynamically). The equilibrium constant for its formation is very large, also
in the vicinity of 1030:
At the same time, this complex anion is labile; that is, the cyanide ligands in the
coordination sphere exchange rapidly with those found free in an aqueous solution.
This exchange rate can be measured when carbon-14-labeled cyanide ions are
placed in solution with the complex.
The labeled cyanides exchange places with their unlabeled counterparts rapidly. In
a matter of seconds, half the unlabeled cyanides are replaced with labeled ligands.
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N K Agnihotri Chem(H) IV Seme (DSC-10) MLNC
The tetracyanonickelate(II) ion, then, is stable but labile. In summary, some
coordination compounds are kinetically inert, whereas others turn out to be labile.
Furthermore, this lability seems to be unrelated to the thermodynamic stability of
the compound.
There is no connection between the thermodynamic stability of a complex and its
lability towards substitution. For example, values of ΔG for Cr3+ and Fe3+ are almost
equal, yet [Cr(OH2)6]3+ (d3) undergoes substitution slowly and [Fe(OH2)6]3+ (high-spin
d5) rapidly. Similarly, although the overall formation constant of [Hg(CN) 4]2- is
greater than that of [Fe(CN)6]4-, the Hg(II) complex rapidly exchanges CN- with
isotopically labelled cyanide, while exchange is extremely slow for [Fe(CN)6]4-.
Explanation of lability and inertness according to VBT :
VBT classifies octahedral complexes into two types. Inner orbital complexes – d2 sp3
and Outer orbital complex – sp3d2.
All outer orbital complexes having sp3d2 hybridization uses high energy 4d orbitals,
and in terms of VBT these bonds are weaker. Therefore, they are generally liable.
Complexes Mn(II), Fe(II),Fe(III),Co(II),Ni(II),Cu(II) and Cr(II) are labile.
Inner orbital complexes generally have d2sp3 hybridization. The inner d orbitals of
metal accommodate the electrons of the metal. If the inner d orbitals are left vacant,
then the complex can associate with an incoming ligand, and the complex is labile (
i.e., less than 3 electrons in d orbitals). Inner orbital complexes of Ti 3+ (d1), V3+(d2)
are labile. If all the inner d orbitals are occupied, then the complex becomes inert
(i.e., more than 3 electrons in d orbitals, Cr3+ (d3)). All inner orbital complexes except
d1 and d2 complexes or having vacant d orbital are inert complexes.
Labile and inert complexes on the basis of CFT: According to CFT the ligand field
splits the d- orbitals into two sets of orbitals, t2g orbitals and eg orbitals. This splitting
leads to a decrease in energy of the system, whose magnitude depends on the
number of d electrons present. If the CFSE value increases by association or
dissociation of a ligand, then the complex is labile. On the other hand, it is inert
when there is a loss in CFSE value. Therefore, any electrons in eg orbitals, complex
is labile.
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N K Agnihotri Chem(H) IV Seme (DSC-10) MLNC
Labile complexes : All complexes in which the central metal atom contains d
electrons in eg orbitals (the dx2–y2 and dz2 orbitals that point toward the six ligands,
for example, [Ga(C2O4)3]3–, d10 (t2g6eg4); [Co(NH3)6]2+, d7(t2g5eg2); [Cu(H2O)6]2+,
d9(t2g6eg3); [Ni(H2O)6]2+, d8(t2g6eg2); [Fe(H2O)6]3+, d5(t2g3eg2).
All complexes that contain less than three d electrons, for example, [Ti(H2O)6]3+, d1;
[V(phen)3]3+, d2; [CaEDTA]2–, do.
Inert complexes: Octahedral low-spin d4, d5, and d6 systems, for example, [Cr(CN)6]3–
(d4 (t2g4), [Fe(CN)6]3–, d5 (t2g5); [Co(NOP2)6]3–, d6 (t2g6); [PtCl6]2–, d6 (t2g6). Octahedral
d3 complexes react relatively slowly, and when the metal ion has an oxidation state
of +3 or higher, their complexes are inert, for example, [Cr(H2O)6]3+ and other
complexes of Cr3+.
By using this classification, one can predict whether an octahedral complex is inert
or labile if one knows its magnetic properties (whether it is high- or low-spin) and
the number of d electrons present in the central atom. The use of crystal field
theory makes it possible to present a more detailed classification than simply inert
and labile.
Mechanism of Labile complexes : (a) All outer orbital complexes (sp3d2) proceed
through the dissociative mechanism (SN1) because of using high energy 4d orbitals.
The dissociative (D) mechanism for the substitution of one ligand for another in an
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N K Agnihotri Chem(H) IV Seme (DSC-10) MLNC
octahedral complex, ML5X (L= inert ligands, X = labile ligand, and Y = incoming
ligand). The mechanism assumes that step (1), the breaking of the M–X bond to form
the five coordinate ML5 intermediate, is the rate-determining step. The rate of the
reaction depends on only the concentration of the original complex, [ML5X].
(b) Inner orbital complexes having vacant d orbitals (less than 3 electrons in d
orbitals, d1 and d2) proceed through the associative mechanism (SN2). The vacant d
orbitals accept the elctrons from incomimg ligand and increase its coordination
number. The associative(A) mechanism for the substitution of one ligand for
another in an octahedral complex, ML5X (L= inert ligands, X = labile ligand, and Y=
incoming ligand). The mechanism assumes that step (1), the formation of an M–Y
bond to form the seven-coordinate ML5XY intermediate, is the rate-determining
step. The rate of the reaction depends on both the concentration of the original
complex, [ML5X], and that of the incoming ligand, [Y].
Complexes that proceed through the above dissociative (SN1) and associative (SN2)
mechanisms are labile. Other complexes require energy (the activation energy is
required to reach an intermediate state) to proceed. Substitution reactions are inert
in these complexes.
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