Coordination Chemistry

Thermodynamic vs Kinetics
Kriteria Reaksi

 Dalam reaksi substitusi ligan, reaksi dapat berlangsung cepat dan yang
lainnya lambat.
 Mekanisme reaksi adalah model hipotetis yang digunakan untuk
memperkiraan suatu reaksi berlangsung dari reaktan ke produk.

Kestabilan Kompleks
1. Stabil
2. Tidak stabil
3. Inert
4. Labil
 Sifat Stabil dan tak stabil termasuk kestabilan termodinamika
 Sedangkan sifat Inert dan labil termasuk kestabilan kinetika
 Contoh 1 :
 Senyawa kompleks tetrasianonikelat(II) dapat mengalami pertukaran ligan secara cepat
(waktu paro sekitar 1 menit).
[Ni(CN)4]2+ + 4C*N-  [Ni(C*N)4]2  4 CN- (t ½ 30 detik)
 Kompleks ini mempunyai harga tetapan disosiasi sangat rendah (Kd = 1 x 10-22)
 Kompleks ini juga mempunyai harga tetapan pembentukan sangat besar (Kf = 1 x 1022).
Kesimpulan :
 Secara kinetika, senyawa kompleks [Ni(CN)4]2- bersifat labil
karena mengalami pergantian (pertukaran) secara cepat dan
terus-menerus).
 Secara termodinamik, senyawa kompleks [Ni(CN)4]2- bersifat
stabil karena tidak mudah terdisosiasi (tidak mudah terurai).
 Contoh 2 :
 Senyawa kompleks [Co(NH3)6]3+ secara spontan dapat berubah menjadi senyawa lebih
stabil [Co(H2O)6]3+ dengan harga tetapan kesetimbangan sangat besar (Keq = 1025).
[Co(NH3)6]3+ + 6H3O+  [Co(H2O)6]3+ + 6NH4+ Keq = 1025
 Pada suhu kamar, reaksi tersebut berlangsung relatif lama (beberapa hari) untuk mencapai
setimbang dan ternyata konsentrasi Co(NH3)6]3+ sangat rendah.
Kesimpulan :
 Kompleks [Co(NH3)6]3+ secara kinetika bersifat inert (lembam) karena
laju pembentukannya relatif lama (perlu beberapa hari).
 Secara termodinamik, kompleks [Co(NH3)6]3+ bersifat tidak stabil karena
secara spontan berubah menjadi spesies lain yang lebih stabil
[Co(H2O)6]3+
 Kompleks yang labil mengalami pertukaran ligan dengan cepat.
 Sebaliknya pada kompleks inert, pertukaran ligan berlangsung dengan
sangat lambat atau bahkan tidak berlangsung sama sekali.
 Suatu kompleks dapat stabil secara termodinamik danmun labil secara
kinetika.
 Suatu kompleks yang tidak stabil bias jadi merupakan kompleks inert.
Sifat kestabilan relatif senyawa kompleks dapat dibedakan menjadi dua hal:
 Kestabilan termodinamik
Membahas energi ikatan logam-ligan, tetapan kestabilan dan variabel turunannya
atau potensial redoks yang mengukur kestabilan tingkat valensi logam.
 Kestabilan kinetika
Membahas sifat senyawa kompleks dalam larutan yang menyangkut laju dan
mekanisme reaksi.
 Kestabilan termodinaik dinyatakan dengan istilah STABIL dan TAK-STABIL
 Kestabilan kinetik dinyatakan dengan istilah INERT (LEMBAM) dan LABIL
 Jadi suatu senyawa kompleks yang bersifat stabil (termodinaik) mungkin bersifat
labil atau mungkin bersifat inert, demikian juga senyawa kompleks tak-stabil
mungkin juga bersifat inert walaupun biasanya bersifat labil.
Tetapan Stabilitas Ion Kompleks
 Pembentukan kompleks dalam suatu larutan berlangsung melalui
sejumlah tahapan.
 Untuk setiap tahapan, tetapan stabilitasnya dapat dituliskan dalam
suatu persamaan.
 Misalkan pembentukan kompleks MLn, terbentuk melalui sejumlah n
tahapan.


Hubungan K dan β


Synthesis of Coordination
Compounds
Kontent
 Ligand Replacement Reactions
 Oxidation-Reduction Reactions
 Partial Decomposition Reactions
Ligand Replacement Reactions
 Many transition metal complexes are synthesized in aqueous solution by displacement of the water
ligands
 For example, we can produce the hexaamminenickel(II) ion by adding an excess of aqueous ammonia to
a solution of the hexaaquanickel(II) ion:

 Ammonia, which is higher than water in the spectrochemical series, readily replaces the water ligands.
 In other words, the nickel-ammonia bond is stronger than the nickel-water bond, and the process is
exothermic
 If we are dealing with a chelating ligand, we find that the equilibrium is driven strongly to the right by
entropy factors as well.
 This situation can be illustrated by the formation of the tris(1,2-diaminoethane)nickel(II) ion from
hexaaquanickel(II) ion:

• In this case, we have a similar enthalpy increase, but there is also a major entropy increase
because the total number of ions and molecules has increased from four to seven.
• It is the entropy factor that results in such strong complex formation by chelating ligands,
behavior that is known as the chelate effect
Oxidation-Reduction Reactions
 Redox reactions are particularly important as a means of synthesizing compounds in “abnormal”
oxidation states.
 High-oxidation-state fluorides can be synthesized by simple combination reactions, for example:
 Other high-oxidation-state compounds and polyatomic ions can be produced using oxidizing agents.

 For example, the red-purple ferrate(VI) ion, FeO42-, can be prepared using the hypochlorite ion in basic
solution:

 The ion can then be precipitated as the barium salt:

 As we mentioned in the previous section, because cobalt(III) complexes are kinetically inert, substitution
reactions for cobalt(III) complexes are usually impractical.
 Cobalt(II) is the dominant oxidation state, and the hexaaqua ion can be used as a reagent to produce a
range of cobalt(III) complexes.
 For example, we can synthesize the hexaamminecobalt(III) ion by the air oxidation of the
hexaamminecobalt(II) complex:
 One method of preparing chromium(III) complexes is by reduction of the dichromate ion.

 In the following example, an oxalic acid–oxalate ion mixture is used as both the reducing agent and the
ligand:

 The large anion can be crystallized as the potassium salt, K3[Cr(C2 O4)3].3H2 O
Partial Decomposition Reactions
 An a few cases, the identity of the coordinating ligands can be changed by gentle heating and
vaporization of the more volatile ligand.
 An example in cobalt(III) chemistry is

 and an example from chromium(III) chemistry is

Coordination Complexes and
the HSAB Concept
Content
 Introduction
 Chemical symbiosis
 Linkage Isomerism and the HSAB Concept
Introduction
 The qualitative divisions into hard/borderline/soft acids of some of the first row transition elements
  These ligand-atom categories generally apply,
irrespective of the other atoms of the ligand.
 For example, all nitrogen-donor ligands of the form NR3
are hard bases, where R is an alkyl group such as methyl
or hydrogen.
 Conversely, all carbon-donor ligands, such as carbon
monoxide and cyanide, are soft bases.
 Chloride is regarded as a hard base, but not as hard as
fluoride or an oxygen-donor ligand.
Classification of the HSAB ligand atoms
into hard (white), borderline (light blue),
and soft (dark blue)
 The HSAB concept accounts for the fact that high oxidation states of metal ions (hard acids) are found
with fluoride or oxide ligands (hard bases).
 It is the low oxidation states (soft acids) that are stabilized by such ligands as the carbon bonded
carbonyl (a soft base).
 To provide a specific example, copper(II) fluoride is known, whereas copper(I) fluoride is not; conversely,
copper(I) iodide is known, whereas copper(II) iodide is not.
 We can use this principle to help us synthesize transition metal compounds in which the metal ions
have abnormal oxidation states.
 For example, iron is usually found in +2 and +3 oxidation states.

 We can prepare a compound of the hard-acid iron(VI) using the hard-base oxide ion to give the ferrate
ion, [FeO4]2-.
 Similarly, we can prepare a compound of soft-acid iron(0) using the soft-base carbonyl molecule to give
pentacarbonyliron(0), [Fe(CO)5]
Chemical Symbiosis
 The HSAB concept is also relevant to reactions of transition metal complexes.
 In particular, there is a general tendency for a complex ion to prefer ligand atoms of the same type.
 Thus, a complex with some hard-base ligands will prefer to add another hard-base ligand.
 Similarly, a complex with soft-base ligands will prefer to add another soft-base ligand.
 This preference for ligands of the same HSAB type is known as chemical symbiosis.
 Cobalt(III) chemistry is particularly useful for the illustration of symbiosis.

 For example, the complex [Co(NH3)5 F]2+ is much more stable in aqueous solution than [Co(NH3)5 I]2+.

 This can be explained in HSAB terms by considering that Co(III) is “hardened” by the presence of five
hard-base ammonia ligands.
 Thus, the soft-base iodide ion is comparatively easily replaced by water (a hard-base ligand) to form
[Co(NH3)5(H2O)]3+.

 On the other hand, [Co(CN)5 I]3- is more stable in water than [Co(CN)5 F]3-.

 It is argued that the five soft-base cyanide ions “soften” the cobalt(III) complex, resulting in a
preference for the soft-base iodide at the sixth coordination site rather than the hard-base water
molecule.
Linkage Isomerism and the HSAB Concept
 A particularly interesting example of the application of the HSAB concept to transition metal complexes
involves linkage isomerism.
 The thiocyanate ion, NCS-, can bond either through the nitrogen atom, in which case it acts as a
borderline base, or through the sulfur atom, in which case it behaves as a soft base.
 We find that in the pentamminethiocyanatocobalt(III) ion, [Co(NH3)5 (NCS)]2+, it is bonded through
nitrogen, as we would expect, since the other ligands are hard bases, while in the
pentacyanothiocyanatocobalt(III) ion, [Co(CN)5(SCN)]3+, coordination is through the sulfur, as is
consistent with the other ligands, cyanides, being soft bases.
 MEKANISME REAKSI SENYAWA KOMPLEKS

Reaksi Substitusi Ligan

 REAKSI SUBSTITUSI LIGAN
Senyawa Kompleks Bilangan Koordinasi enam
Reaksi
Y + M-X  M-Y  X
Ket :
X  Gugus tersingkir (leaving group)
Y  Gugus penyingkir (entering group)
 TIPE MEKANISME REAKSI SUBSTITUSI
LIGAN
Mekanisme SN1 (Disosiatif)
[L5MX]n+  [L5M]n  [L5MY]n
Mekanisme SN2 (Asosiatif)
 Dissociative Mechanism
ML5X + Y ML5Y + X

Step 1. Dissociation of X to yield a 5 coordinate intermediate.

K1
ML5X ML5 + X M-X bond is broken

L L Slow and rate determining

L L L
L M M The rate of D is only depends
L L L on the conc. of ML5X
L
Trigonal Bipyramidal Square Pyramidal

Step 2. Coordination of Y to the ML5 intermediate.

K2
ML5 + Y ML5Y This mechanism is independent of [Y]
fast
The rate law for this process is rate = K1[ML5X] (the units of K1 are sec-1)
If we find a reaction follows this rate law we conclude it is dissociative.
Principal mechanisms of ligand exchange in octahedral complexes

Dissociative
k1
ML X ML 5
+ X
5
slow r = k 1 [ML 5 X]
k2
+Y
ML 5
Y
fast

Associative
k1
ML 5
X + Y ML 5 XY
slow r = k 1 [ML 5 X][Y]
k2
-X
ML 5 Y
fast
 Associative Mechanism
ML5X + Y ML5Y + X

Step 1. Collision of ML5X with Y to yield a 7-coordinate intermediate. (slow)

K1
ML5X + Y ML5XY (slow, rate determining)

X Y
L
L L L
M L M
L X
L Y
L
L
L

Capped Pentagonal
Octahedron Bipyramid
Step 2. Cleavage of the M-X bond. (fast)

ML5XY ML5Y + X (fast)

The rate law for this process is rate = K1[ML5X][Y] (the units of K1 are sec-1Mole-1)
If we find a reaction follows this rate law we conclude it is associative.
 Substitution reactions

ML n + L' ML n-1 L' + 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 Gf <0)

Inert Intermediate Labile

d 3 , low spin d 4-d 6 & d 8 d 8 (high spin) d 1 , d 2 , low spin d 4 - d 6 & d 7 - d 10

 Mechanisms of ligand exchange reactions
in octahedral complexes

ML n
X + Y ML n Y + X

Dissociative (D) Associative (A)

ML n X ML n Y ML X ML Y
n n

X ML n Y Y X
ML n XY

Interchange (I)
ML n
X ML n
Y

Y ° X
[ML n
]

Ia if association X Y Id if dissociation
is more important is more important