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Reaksi

Senyawa Anorganik

Prinsip-prinsip dasar / hukum dasar reaksi

Reaksi

Perubahan atau transformasi


Diamati dengan

Spektroskopi
Struktur Energi

Struktur I Struktur II Energi I Energi II


cepat
Reaksi
lambat Dapat ditentukan mekanismenya

Ada 2 aspek reaksi :


1. Aspek Termodinamika : Energi ikat, ∆H, ∆G, ∆S, potensial redoks, K stabilitas
2. Aspek kinetika : laju reaksi, mekanisme reaksi, besaran-besaran TD
yang menyangkut keadaan intermediet (madya)
(madya),
kompleks teraktivasi.

Reaksi terjadi apabila struktur yang baru > kestabilannya

Bandingkan : KNO3 padat dicampur NaCl padat dalam air dengan

AgNO3 pdt dicampur NaCl padat dalam air


Introduction to Inorganic Reaction Mechanisms
Scope of the course
•Limited to solution reactions
•"classical inorganic" reactions which occur at metal centres in
coordination complexes
(mechanisms of organometallic reactions given on the other subject)

Elementary Reaction Kinetics and Mechanism


Transition State Theory
Note: only applies when transition state in equilibrium with the
reactants
does not apply in reactions which are at diffusion controlled limit
Therefore: fast reactions are favoured by

Note: since the rate is exponentially dependent on both ∆ S‡ and


∆ Eact, small rate changes are "not significant" for the
interpretation
p of mechanism with these veryy crude theories.
Effects of Pressure on the Rate of Reactions
Measurements of Rates of Reactions

i t" species
inert"
•" i i.e.
i t1/2 > 1 min
i
We can use classical static techniques, e.g. light absorption, pH measurements
•"labile" species:
p i.e. t1/2 ca. 1 min-1ms
Use stop flow measurements, rapid mixing, fast spectroscopy
•"rapid"reactions: -relaxation techniques + fast spectrophotometry
General Comments:
We cannot conclude a mechanism from a rate law !
eg
e.g.

(i) involvement of solvent (pseudo-first order behaviour)


(ii) complex reactions with only one rate limiting step.
Fi ll remember
Finally b you can only l disprove
di a mechanism
h i you can
never prove a mechanism.
A rate law can at best only be consistent with a mechanistic scheme, it
can never prove it.
it

Definitions:
(1) "Lability"
Lability and "Inert"
Inert are kinetic terms !!
(2) "Stable" and "Unstable" are thermodynamic statements
(3) "Intimate" Mechanism refers to the details of the mechanism
on the molecular scale.
Substitution at Square Planar Metal Complexes

For further information concerning the elements, why not try the On-line
Periodic Table from the University of Sheffield - Web-Elements
Examples of Square Planar Transition Metal Complexes:
Ni(II) (mainly d8) Rh(I) Pd(II) Ir(I) Pt(II) Au(III)
General Rate Law:
Factors Which Affect The Rate Of Substitution
1. Role of the Entering Group
2. The Role of The Leaving Group
3 The Nature of the Other Ligands in the Complex
3.
4. Effect of the Metal Centre

An illustration of the importance of solvent on the substitution


pathways
p y for square
q planar
p reaction centres
3. The Nature of other Ligands in the Complex
The Trans Ligands
Definition;
The trans effect is best defined as the effect of a coordinated ligand
upon the rate of substitution of ligands opposite to it.
For example, in the substitution reactions of Pt(II) square planar
complexes, labilizing effect is in the order;
H2O ~ OH- ~ NH3 ~ amines ~ Cl- < SCN- ~ I- < CH3- < Phosphines ~
H- < Olefins < CO ~ CN-
Note that the "labilizing effect" is used to emphasise the fact that this
is a kinetic phenomenon.
Note that the "labilizing
g effect" is used to emphasise
p the fact that this is a
kinetic phenomenon.

This labilization may arise because of destabilisation (a thermodynamic term)


of the ground state and/or a stabilisation of the transition state.
The trans influence is purely a thermodynamic phenomenon. That is,
ligands can influence the ground state properties of groups to which
they are trans. Such properties include;
(i) Metal-Ligand bond lengths
(ii) Vibration frequency or force constants
(iii) NMR coupling constants
The trans influence series based on structural data, has been given as;
R- ~ H- >= PR3 > CO ~ C=C ~ Cl- ~ NH3

* The cis ligands


In cases where a relatively poor nucleophile act as the entering group
N t Compare
Note: C with
ith th
the trans
t i below,
series b l it acts
t iin th
the same way.
The Intimate Mechanism for Substitution at Square Planar
Complexes

The assiciative pathways utilized in the substitution of one ligand for


another at a square planar reaction centre
TYPICAL REACTION COORDINATES
The 1st order dependence of the rate of the reaction on:
the concentration of the substrate
the concentration entering reagent
Indicates that these complexes undergo substitution of ligands by a
bimolecular mechanism.
Some important points concerning the "intimate" mechanism
Profile A applies when the energies of the reactants and products are
almost equal
equal, and in which the energies of the transition states are almost
equal.
Profile B is appropriate to a reaction for which the bond breaking is rate
determining (d mechanism from the intermediate)
Profile C depicts the situation when bond forming is rate determining, a
situation in which the entering group (Y) lies higher in the trans effect
series than the leaving group.
In a few cases the intermediate is reasonable stable and so lies at lower
energy than the products.
For example;
For example;
p ;
A reaction profile for a reaction where a quasi-stable intermediate is formed before
the transition state: bond breaking in the five-coordinate
five coordinate intermediate is more
important than bond making to form the intermediate
General Substitution Reactions of Octahedral Complexes
Studies on octahedral complexes have largely been limited to two types of
reaction:
•Replacement of coordinated solvent ( eg water). Perhaps the most
thoroughly studies replacement reactions of this type is the formation of a
complex
l iion ffrom a h
hydrated
d t d metal
t l iion iin solution.
l ti

•Anation: When the entering group is an ion the reaction is called anation.
•Solvolysis. Since the majority of such reactions have been carried out in
•Solvolysis
aqueous solution, hydrolysis is a more appropriate term. Hydrolysis reactions
have been done under acidic or basic conditions.
Electron Transfer Reactions
Outer Sphere Electron Transfer
Electron transfer reactions may occur by either of both of two mechanisms:
outer or inner sphere mechanisms. In principle all outer sphere mechanism
involves electron transfer from reductant to oxidant with the coordination
shells or spheres of each staying intact. That is one reactant becomes
involved in the outer or second coordination sphere of the other reactant
and an electron flows from the reductant to oxidant
oxidant. Such a mechanism is
established when rapid electron transfer occurs between two substitution-
inert complexes.
Inner Sphere Electron Transfer
A inner
An i sphere
h mechanism
h i iis one iin which
hi h th
the reactant
t t and
d oxidant
id t share
h a
ligand in their inner or primary coordination spheres the electron being
transferred across a bridging
g gg group.
p
Inner Sphere Electron Transfer
The reduction of hexaamminecobalt(3+) by hexaaquochromium(2+) occurs
slowly (k = 10-3 M-1sec-1) by an outer sphere mechanism.

However, if one ammonia ligand on Co(III) is substituted by Cl-, reaction now


occurs with a substantially greater rate (k = 6 x 105 M-1 sec-1).
4 categories based on rate of exchange coordinated water :

1. Extreemly fast (1st order rate constant 108 s-1) alkali metas and alkali earth
metal
2. Exchange water is fast (1st order rate constant 105 - 108 s-1) dipositive
transition metal, Mg2+, tripositive lanthanides
3. Relative slow. (1st order rate constant 1 - 104 s-1) tripositive transition metal,
Be2+, Al3+
4 Slow , for only inert complexes (1st order rate constant 10-1 – 10-9 s-1) Cr3+,
4.
Ru3+, Pt2+, Co3+
Senyawa kompleks :
Senyawa yang dalam larutannya terionisasi mempunyai ion kompleks

Ion kompleks :
• Ion yang terdiri dari atom pusat dan dikelilingi ligand
• Ikatannya kovelen koordinasi
• Logamnya mempunyai valensi sekunder

Valensi sekunder ((= bil koordinasi)) menentukan bentuk molekul dari


kompleks
tidak terionisasi
Velensi primer menentukan muatan ion kompleks
terionisasi
STEREOKIMIA DAN ISOMER

Stereokimia : Bidang ilmu kimia yang mempelajari tentang struktur ruang


senyawa kimia

Isomer : Rumus molekul sama struktur berbeda ( isomer geometri dan


isomer ruang)

Bilangan koordinasi 4 :
Tetrahedral : tidak mempunyai isomer
Planar MA2B2 (cis dan trans)

Isomer geometri : struktur geometrinya sama tetapi tatanan ligand dalam


struktur berbeda

MABCD : isomer geometrinya ada 3


kemungkinan struktur yang lain square piramidal
Cara membedakan isomer cis dan trans
1. Fisika : lihat momen dipolnya
Pt(NH3)2Cl2
A B B A
M M
A B A B
Cis momen dipolnya ≠ 0
trans momen dipolnya = 0
2. Spektroskopi : IR spektra
Dari stretching (mulur pendek spt per pegas)
Jenis stretching :
M-A M-A
M-B M-B
M-A (B) M-A (A)
M-B (A) M-B (B)
peak lebih rumit peak sederhana
3. Kimia : dengan mereaksikan dengan senyawa kimia
NH3 NH3
K2[PtCl4] [α-Pt(NH3)2Cl2] [Pt(NH3)4Cl2]
AgNO3 + HCl
+ H2C2O4
[β-Pt(NH3)2Cl2] trans
[Pt(NH3)2C2O4]
Non elektrolit AgNO3
+
H2C2O4
NH3 O

Pt C O [Pt(NH3)2(OOCCOOH)2]
Dibasic acid
NH3 C O
O O
NH3 O O
C
O Pt C
C O OH
C NH3
O
OH
Isomer-isomer yang lain :
1 Isomer
1. I ligand
li d : suatu
t seny kkompleks
l k d
dgn liligan yang mempunyaii rumus
kimia sama tetapi berbeda strukturnya.
Misalnya : 1,2 diaminopropana dan 1,3 diamino propana
o,m, p-toluidine
2. Isomer ionisasi :
Stuktur kompleks sama hasil ionisasi berbeda

Misalnya : [Co(NH3)5SO4]Br ⇋ [Co(NH3)5SO4]+ + Br-

[Co(NH3)5Br] SO4 ֕ [Co(NH3)5Br]2+ + SO4 22-


Sebab berbeda ligan dalam inner sphere
3. Isomer pelarut : solvatasi
Senyawa kompleks bila dilarutkan oleh air (isomer hidrat)
[Cr(H2O)6]Cl3 ⇋ [Cr(H2O)6] 3+ + 3 Cl- ungu
[[Cr(H
( 2O))5Cl]Cl
] 2 ֕ [[Cr(H
( 2O))5Cl]] 2+ + 2 Cl- hijau
j muda
4. Isomer koordinat
Garam yang terbentuk dari kation dan anion kompleks yang menunjukkan
sifat isomerisasi dengan melalui penggantian satu ligan atau lebih dari kation
ke anion.
Mi l
Misalnya :
[Co(NH3)6]3+[Cr(CN)6]3- dan [Co(CN)6]3-[Cr(NH3)6]3+
Tata susunan ligan yang terikat oleh atom pusat adalah berbeda
Atom pusatnya berbeda
Reaksi pada square planar :
S b tit i nukleofilik
Substitusi kl filik
Dikenal di dalam kimia organik
Substitusi elektrofilik
Addisi oksidatif
Eliminasi reduktif
N3-
(
PtMeCl(PMe 2Ph))2 PtMe(N )(PMe2Ph))2 + Cl-
( 3)(
Nu Subst

Cl2
PtCl2(PMe2Ph)2 + MeHgCl
El Subst

PtMeCl3((PMe2Ph))2 PtCl2(PMe2Ph)2 + MeCl

Add Ox El red