Bag. 2 Stabilitas Dan Ketidakstabilan

STABILITY,
INSTABILITY, LABILITY
AND INERTNESS
in coordination compounds
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Substitution reactions
MLn + L' MLn-1L' + L
Labile complexes <==> Fast substitution reactions (< few min)

Inert complexes <==> Slow substitution reactions (>h)
a kinetic concept
Not to be confused with

stable and unstable (a thermodynamic concept DGf <0)
Inert Intermediate Labile

d3, low spin d4-d6& d8 d8 (high spin) d1, d2, low spin d4-d6& d7-d10
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Inert & Labile Complexes
– labile => exchange t1/2 less than 1 min. at room T
– inert => exchange t1/2 more than 1 min. at room T
According to TAUBE
Labile complexes:
1. if d e-s are in eg*
[Co(NH3)6] 2+ d7 (t2g5, eg2)
[Cu(OH2)6]2+ d9 (t2g6, eg3)
[Fe(OH2)6]3+ d5 (t2g3, eg2)

2. if less than 3 e-s in t2g
[Ti(OH2)3]3+ d1 (t2g1, eg0)
[V(phen)6]3+ d2 (t2g2, eg0)
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Inert complexes:
1. Octahedral d3
[Cr(OH2)3]3+ d3 (t2g3, eg0)
2. Low spin d4, d5, d6

[Fe(CN)6]3- d5 octahedral
[Co(NO2)6]3- d6 octahedral
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[Ni(CN)4]2- stable complex, tetapi cepat berubah menjadi
kompleks yang lain
[Ni(OH2)6]2+ + 4CN- [Ni(CN)4]2- + 6 H2O
fast
[Ni(CN)4]2- + 4C14N- [Ni(C14N)4]2- + 4CN- t ½ = 30 s
[Mn(CN)6]3- intermediate t½ =1h
[Cr(CN)6]3- inert t ½ = 24 days
[Co(NH3)6]3+ not stable in acid solution, tetapi perubahannya

lambat, not stable complex but inert
[Co(NH3)6]3+ + 6 H3 O + slow [Co(OH ) ]3+ + 6 NH4+

2 6
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Compounds such as these that react rapidly are called labile. In
many cases, exchange of one ligand for another can take place in
the time of mixing the solutions. Taube' has suggested a reaction
half-life (the time of disappearance of half the initial compound) of
one minute or less as the criterion for lability.
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Compound react more slowly are called inert.
A species such as [Fe(H2O)5(F)]2+ is very stable (has a
large equilibrium constant for formation), but it is also
labile. On the other hand, Hexaaminecobalt(3+) is
thermodynamically unstable in acid and can decompose to
the equilibrium mixture on the right but it reacts very
slowly (has a very high activation energy) and is
therefore called inert or robust.
Complexes that undergo ligand replacement

rapidly are said to be labile
Complexes that undergo ligand replacement very
slowly are said to be inert
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β4 = K1 + K2 + K3 + K4
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[Cu(OH2 )3 NH3 ]2 [H 2O]
K1  2
[Cu(OH2 ) 4 ] [NH3 ]
[Cu(OH2 ) 2 (NH3 ) 2 ]2 [H 2O]
K2  2
[Cu(OH2 )3 (NH3 )] [NH3 ]
[Cu(OH2 )(NH3 )3 ]2 [H 2O]

K3  2
[Cu(OH2 ) 2 (NH3 ) 2 ] [NH3 ]
[Cu(NH3 ) 4 ]2 [H 2O]
K4  2
[Cu(OH2 )(NH3 )3 ] [NH3 ]
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• Stabilitas kompleks ditentukan oleh
energi reaksi yaitu perbedaan antara
energi hasil reaksi dan peraksi.
Energi besar, kompleks stabil
• Labilitas kompleks ditentukan oleh
perbedaan energi antara senyawa
awal dengan kompleks teraktifasi.
Energi besar reaksi lambat, kompleks
inert
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Inert and labile complexes
Some common thermodynamic and kinetic profiles
Exothermic Exothermic Endothermic

(favored, large K) (favored, large K) (disfavored, small K)
Large Ea, slow reaction Large Ea, slow reaction Small Ea, fast reaction
Stable intermediate
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Labile or inert?
L
L L
M
L L
Ea
L
L L
L M
L L L L
M X
L L
X
DG
LFAE = LFSE(sq pyr) - LFSE(oct)
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Why are some configurations inert and some are labile?
Inert !
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bidentate ligands
bound to cobalt.
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hexadentate ligand
bound to cobalt.
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THE KINETIC CHELATE EFFECT
(1)
(2)
(3)
(4)
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Substitution for a chelated ligand is generally a slower reaction than that for a
similar monodentate ligand.
Explanations for this effect center on two factors:
- the increased energy needed to remove the first bound atom
- and the probability of a reversal of this first step.
The reaction must have two dissociation steps for a bidentate ligand, one
for each bound atom (the addition of water in Steps 2 and 4 is likely to be
fast, because of its high concentration):
The first dissociation (1) is expected to be slower than a similar dissociation of

ammonia because the ligand must bend and rotate to move the free amine
group away from the metal.
The second dissociation (3) is likely to be slow because the concentration of

the intermediate is low and because the first dissociation can readily reverse.
The uncoordinated nitrogen is held near the metal by the rest of the ligand,
making reattachment more likely. Overall, this kinetic chelate effect reduces
the rates of aquation reactions by factors from 20 to 105.
8/26/2014
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Hydrolysis reactions
Hydrolysis reaction of complexes in base solution can take place via
associative mechanism, but intermediate with 7 coordination number is
not stable
Rate of reaction:
 [new  complex]
 kB[in  complex][O H  ]
dt
[(NH3)5CoCl]+2 + OH- [(NH3)5CoCl (OH-]]+2
[(NH3)5CoOH]+2
Another mechanism was proposed: dissociative mechanism in the

presence of hydroxide ion, forming an intermediate with 5 coordination
number
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fast
[(NH3)5 CoCl]+2 + OH- [(NH3)4Co(NH2)Cl]+ + H 2O
slow
[(NH3)4Co(NH2)Cl]+ [(NH3)4Co(NH2)]+2 + Cl-
fast
[(NH3)4Co(NH2)]+2 + H 2O [(NH3)5Co OH]+2
The conjugate base mechanism (SN 1 CB)

will occurred if the ligands in certain complex
have the protons that can be protonated
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Hydrolysis reactions
Dissociative mechanisms can lead to single-product reactions with either

retention of configuration or a change of configuration, depending on the
circumstances. For example, base hydrolysis of Λ-cis-[Co(en)2Cl2]+ in
dilute (<0.01 M) hydroxide yields Λ -cis-[Co(en)2(OH)2]+, but in more
concentrated (>0.25 M) hydroxide it gives Δ-cis-[Co(en)2(OH)2]+
8/26/2014
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A conjugate base mechanism is expected in both cases, with the hydroxide
removing a proton from an ethylenediamine nitrogen, followed by loss of the
chloride trans to the deprotonated nitrogen. In the more concentrated base, the
higher concentration of ion pairs ([Co(en)2Cl2]+.OH-) is assumed to result in a water
molecule (from the OH- and the H+ removed from ethylenediamine) positioned for
easy addition with inversion of the chiral center.
8/26/2014
Rahmayeni

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STABILITY,

Labile complexes <==> Fast substitution reactions (< few min)

Not to be confused with

Inert Intermediate Labile

[Cu(OH2)6]2+ d9 (t2g6, eg3)

[Fe(OH2)6]3+ d5 (t2g3, eg2)

[Ti(OH2)3]3+ d1 (t2g1, eg0)

[V(phen)6]3+ d2 (t2g2, eg0)

2. Low spin d4, d5, d6

[Ni(OH2)6]2+ + 4CN- [Ni(CN)4]2- + 6 H2O

[Mn(CN)6]3- intermediate t½ =1h

[Cr(CN)6]3- inert t ½ = 24 days

[Co(NH3)6]3+ not stable in acid solution, tetapi perubahannya

[Co(NH3)6]3+ + 6 H3 O + slow [Co(OH ) ]3+ + 6 NH4+

Complexes that undergo ligand replacement

[Cu(OH2 )(NH3 )3 ]2 [H 2O]

Exothermic Exothermic Endothermic

LFAE = LFSE(sq pyr) - LFSE(oct)

The first dissociation (1) is expected to be slower than a similar dissociation of

The second dissociation (3) is likely to be slow because the concentration of

[(NH3)5CoCl]+2 + OH- [(NH3)5CoCl (OH-]]+2

Another mechanism was proposed: dissociative mechanism in the

The conjugate base mechanism (SN 1 CB)

Dissociative mechanisms can lead to single-product reactions with either

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