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 of mechanism with these very crude theories. p y Effects of Pressure on the Rate of Reactions

Measurements of Rates of Reactions
•"

inert" species i t1/2 > 1 min i t" i i.e. i

We can use classical static techniques, e.g. light absorption, pH measurements •"labile" species: i.e. t1/2 ca. 1 min-1ms p 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 !
e.g. eg

(i) involvement of solvent (pseudo-first order behaviour) (ii) complex reactions with only one rate limiting step. Finally Fi ll remember you can only disprove a mechanism you can b l di h i 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" and "Inert" are kinetic terms !! Lability Inert (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. 3 The Nature of the Other Ligands in the Complex 4. Effect of the Metal Centre

An illustration of the importance of solvent on the substitution p pathways for square planar reaction centres y q p

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 ~ CNNote that the "labilizing effect" is used to emphasise the fact that this is a kinetic phenomenon.

Note that the "labilizing effect" is used to emphasise the fact that this is a g p 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

Note: Compare with th t N t C ith the trans series b l i below, it acts i th same way. t in the

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 and in which the energies of the transition states are almost equal, 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 intermediate is more five coordinate 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 i f l ion from a h d t d metal i i solution. hydrated t l ion in l ti

•Anation: When the entering group is an ion the reaction is called anation.

•Solvolysis. •Solvolysis Since the majority of such reactions have been carried out in 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 Such a mechanism is oxidant. established when rapid electron transfer occurs between two substitutioninert complexes.

Inner Sphere Electron Transfer An i A inner sphere mechanism i one i which th reactant and oxidant share a h h i is in hi h the t t d id t h ligand in their inner or primary coordination spheres the electron being transferred across a bridging g p g g group.

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. 4 Slow , for only inert complexes (1st order rate constant 10-1 – 10-9 s-1) Cr3+, 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 M A B A B B M B A

Cis momen dipolnya ≠ 0 trans momen dipolnya = 0 2. Spektroskopi : IR spektra Dari stretching (mulur pendek spt per pegas) Jenis stretching : M-A M-B M-A (B) M-B (A) peak lebih rumit M-A M-B M-A (A) M-B (B) 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

+

NH3 Pt NH3 O

O C O C O O C OH C O O

AgNO3 H2C2O4

[Pt(NH3)2(OOCCOOH)2]
Dibasic acid

NH3 Pt

O

O C C

O OH

NH3

Isomer-isomer yang lain : 1. Isomer ligand : suatu seny k 1 I li d t kompleks d li l k dgn ligan yang mempunyai rumus i 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)5Br] SO4

[Co(NH3)5SO4]+ + Br2 [Co(NH3)5Br]2+ + SO4 2-

Sebab berbeda ligan dalam inner sphere 3. Isomer pelarut : solvatasi Senyawa kompleks bila dilarutkan oleh air (isomer hidrat) [Cr(H2O)6]Cl3 [ ( [Cr(H2O)5Cl]Cl2 ) ]

[Cr(H2O)6] 3+ + 3 Cl[ ( [Cr(H2O)5Cl] 2+ + 2 Cl) ]

ungu hijau muda j

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. Misalnya : Mi l [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 : Substitusi kl filik S b tit i nukleofilik Substitusi elektrofilik Addisi oksidatif Eliminasi reduktif ( ) PtMeCl(PMe2Ph)2 N3PtMe(N3)(PMe2Ph)2 + Cl( )( )
Nu Subst

Dikenal di dalam kimia organik

Cl2 PtCl2(PMe2Ph)2 + MeHgCl
El Subst

PtMeCl3(PMe2Ph)2 ( )
Add Ox

PtCl2(PMe2Ph)2
El red

+ MeCl

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