Professional Documents
Culture Documents
Senyawa Anorganik
Reaksi
Spektroskopi
Struktur Energi
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.
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
•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.
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
Bilangan koordinasi 4 :
Tetrahedral : tidak mempunyai isomer
Planar MA2B2 (cis dan trans)
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
Cl2
PtCl2(PMe2Ph)2 + MeHgCl
El Subst
Add Ox El red