Nama Kelompok : 1. 2. 3. 4.

Siti Aminah Gustina Nuzula Syelli Ayu Friani Diah Syafitri

Reaksi Eliminasi
Merupakan reaksi dimana substrat kehilangan unsur dari molekul kecil seperti HCl, H2O atau Cl2 selama reaksi pembentukan produk.

Alpha-Hydride Elimination Alpha-hydride elimination is the transfer of a hydride (hydrogen atom) from the alpha-position on a ligand to the metal center. The process can be thought of as a type of oxidative addition reaction as the metal center is oxidized by two electrons (Eq 1). As the reaction involves a formal oxidation of the metal, alpha-elimination can not occur in a d0 or d1 metal complex. In these cases, a variant called alpha-abstraction can occur. Alpha-abstraction does not result in a change of oxidation state and the alpha-hydrogen is transferred directly to an adjacent ligand instead of the metal center (Eq 2):

Alpha-abstraction is a common method for synthesizing high oxidation state alkylidene and alkylidyne complexes. While alpha-elimination requires an open coordination site on the metal complex, alpha-abstraction does not. As shown below,

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alpha-abstraction may be induced by a steric crowding of the metal; the abstraction can occur spontaneously or be induced by addition of a donor ligand such as a phosphine:

The mechanism of both alpha-elimination and alpha-abstraction proceeds through the same sort of four-center transition state as beta-hydride elimination or sigma bond metathesis. Alpha elimination/abstraction can occur when the metal contains both alpha and beta hydrogens, but is most common when beta-hydride elimination is blocked. The microscopic reverse of a alpha-hydride abstraction would be a called a carbonhydrogen bond activation in which the C-H bond adds across a metal-ligand bond. In practice, such activations are rare, although highly desirable from the context of functionalization of hydrocarbons. A third type of elimination reaction encountered with alkyl ligands is the delta elimination reaction.

Beta-Hydride Elimination Beta-hydride elimination is a common reaction in organometallic chemistry. The reaction is simply the transfer of a hydride (hydrogen atom) from the beta-position on a ligand to the metal center. While most common in alkyl complexes, it is also observed with other ligands, one example being alkoxide ligands bound to late transition metal complexes:

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The mechanism shown indicates a four-center transition state in which the hydride is transferred to the metal. In some cases, the unsaturated fragment that is formed will remain bound to the metal and in other cases it will either not bind or be displaced by a stronger donor ligand. An important prerequisite for beta-hydride elimination is the presence of an open coordination site on the metal complex. If no open site is available, then it will be necessary to displace a ligand before the reaction can occur. In addition, the metal complex will usually have less than 18 electrons, otherwise a 20 electron olefin-hydride would be the immediate product. The microscopic reverse of a beta-hydride elimination is called an olefin insertion reaction. In many systems there is a rapid, reversible equilibrium between the alkyl complex and the alkene-hydride that results from beta-elimination. Beta-elimination is a very important chain termination step in the polymerization of olefins, in the hydrozirconation reaction and in a variety of catalytic processes. In order to prevent beta-elimination from taking place, one can use alkyls that:
o o o

Do not contain beta-hydrogens. Are oriented so that the beta position can not access the metal center. Would give an unstable alkene as the product.

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A few of these are shown below:

While these approaches can successfully block beta-hydride elimination, the metal complex may still be able to undergo other intramolecular reactions such as alphaelimination or delta elimination.

Other Hydride Elimination While beta-hydride and alpha-elimination reactions are the most common

elimination reactions in transition metal chemistry, other elimination modes are also possible. Eliminations from the gamma, delta or epsilon position of a coordinated ligand are also observed, most commonly with late transition metal complexes but also in complexes that are sterically and electronically unsaturated. A few examples of each of these are shown below.

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As shown in the above examples, this mode of reactivity is an important method for the synthesis of late transition metal metallacycles and is therefore sometimes referred to as cyclometallation. The last example shown is called a orthometallation reaction as it involves the activation of a C-H bond in the ortho position of an aryl group. This turns out to be an important degradation pathway in industrially desirable catalysts that contain phosphine ligands. The mechanism of these reactions is essentially no different than that of an alphaelimination which, in turn, is really just a variant of the oxidative additionreaction.

Mekanisme reaksi E1 Mekanisme reaksi E1 merupakan alternatif dari mekanisme reaksi SN1. Karbokation dapat memberikan sebuah proton kepada suatu basa dalam reaksi eliminasi.
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Mekanisme reaksi E1 terdiri dari dua tahap. Perhatikan contoh berikut ini. Tahap 1. Tahap 1 reaksi E1 berjalan lambat.

Tahap 2. Tahap 2 reaksi E1 berjalan cepat.

Diagram perubahan energi reaksi E1

Mekanisme reaksi E2 Reaksi E2 terjadi melalui satu tahap, secara serentak. Semua ikatan terputus dan terbentuk tanpa pembentukan suatu intermediet. Reaksi E2 menggunakan basa kuat seperti -OH, -OR, dan juga membutuhkan kalor. Dengan memanaskan alkil halida dalam KOH, CH3CH2ONa.

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Diagram perubahan energi reaksi E2

Stereokimia Produk Reaksi E2 Dalam keadaan transisi suatu reaksi eliminasi E2, basa yang menyerang dan gugus yang pergi umumnya sejauh meungkin, atau anti. Karena inilah maka eliminasi E2 seringkali dirujuk sebagai anti-eliminasi.

Anti periplanar -kebanyakan mengadopsi konformasi lebih mudah molekul dapat

syn periplanar tetapi eklips

Contoh :

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Mekanisme Reaksi E1 cB

Dalam mekanisme E1cB, urutan pelepasan terbalik: proton dieliminasi terlebih dahulu.

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Daftar Pustaka : Susanti, Elfi. Reaksi Eliminasi. Online : (http://www.slideshare.net/elfisusanti/reaksieliminasi-1961874) http://www.chem.ucla.edu/harding/IGOC/B/beta_elimination.html http://www.ilmukimia.org/2013/04/perbedaan-mekanisme-sn2-sn1-e1-dan-e2.html http://www.slideshare.net/AnniqueRomance/reaksi-eliminasi-t

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