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Concept
Oxidative addition
Summary
Oxidative addition and reductive elimination are two important and related classes of reactions in organometallic chemistry. Oxidative addition is a process that increases both the oxidation state and coordination number of a metal centre. Oxidative addition is often a step in catalytic cycles, in conjunction with its reverse reaction, reductive elimination.
For transition metals, oxidative reaction results in the decrease in the dn to a configuration with fewer electrons, often 2e fewer. Oxidative addition is favored for metals that are (i) basic and/or (ii) easily oxidized. Metals with a relatively low oxidation state often satisfy one of these requirements, but even high oxidation state metals undergo oxidative addition, as illustrated by the oxidation of Pt(II) with chlorine:
[PtCl4]2− + Cl2 → [PtCl6]2−
In classical organometallic chemistry, the formal oxidation state of the metal and the electron count of the complex both increase by two. One-electron changes are also possible and in fact some oxidative addition reactions proceed via series of 1e changes. Although oxidative additions can occur with the insertion of a metal into many different substrates, oxidative additions are most commonly seen with H–H, H–X, and C–X bonds because these substrates are most relevant to commercial applications.
Oxidative addition requires that the metal complex have a vacant coordination site. For this reason, oxidative additions are common for four- and five-coordinate complexes.
Reductive elimination is the reverse of oxidative addition. Reductive elimination is favored when the newly formed X–Y bond is strong. For reductive elimination to occur the two groups (X and Y) should be mutually adjacent on the metal's coordination sphere. Reductive elimination is the key product-releasing step of several reactions that form C–H and C–C bonds.
Oxidative additions proceed via many pathways that depend on the metal center and the substrates.
Oxidative additions of nonpolar substrates such as hydrogen and hydrocarbons appear to proceed via concerted pathways.
Official source
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Related concepts (16)
Reductive elimination
Reductive elimination is an elementary step in organometallic chemistry in which the oxidation state of the metal center decreases while forming a new covalent bond between two ligands. It is the microscopic reverse of oxidative addition, and is often the product-forming step in many catalytic processes. Since oxidative addition and reductive elimination are reverse reactions, the same mechanisms apply for both processes, and the product equilibrium depends on the thermodynamics of both directions.
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