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.
Role in transition metal chemistry
For transition metals, oxidative reaction results in the decrease in the d<sup>n</sup> 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:
:[PtCl<sub>4</sub>]<sup>2−</sup> + Cl<sub>2</sub> → [PtCl<sub>6</sub>]<sup>2−</sup>
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.
A representative example is the reaction of hydrogen with Vaska's complex, trans-IrCl(CO)[P(C<sub>6</sub>H<sub>5</sub>)<sub>3</sub>]<sub>2</sub>. In this transformation, iridium changes its formal oxidation state from +1 to +3. The product is formally bound to three anions: one chloride and two hydride ligands. As shown below, the initial metal complex has 16 valence electrons and a coordination number of four whereas the product is a six-coordinate 18 electron complex.
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Formation of a trigonal bipyramidal dihydrogen intermediate is followed by cleavage of the H–H bond, due to electron back donation into the H–H σ*-orbital, i.e. a sigma complex. This system is also in chemical equilibrium, with the reverse reaction proceeding by the elimination of hydrogen gas with simultaneous reduction of the metal center.
The electron back donation into the H–H σ*-orbital to cleave the H–H bond causes electron-rich metals to favor this reaction.
Radical
In addition to undergoing S<sub>N</sub>2-type reactions, alkyl halides and similar substrates can add to a metal center via a radical mechanism, although some details remain controversial.
;Initiation
:[[Azobisisobutyronitrile|[(CH<sub>3</sub>)<sub>2</sub>C(CN)N]<sub>2</sub>]] → 2 (CH<sub>3</sub>)<sub>2</sub>(CN)C<sup>•</sup> + N<sub>2</sub>
:(CH<sub>3</sub>)<sub>2</sub>(CN)C<sup>•</sup> + PhBr → (CH<sub>3</sub>)<sub>2</sub>(CN)CBr + Ph<sup>•</sup>
;Propagation
:Ph<sup>•</sup> + [Pt(PPh<sub>3</sub>)<sub>2</sub>] → [Pt(PPh<sub>3</sub>)<sub>2</sub>Ph]<sup>•</sup>
:[Pt(PPh<sub>3</sub>)<sub>2</sub>Ph]<sup>•</sup> + PhBr → [Pt(PPh<sub>3</sub>)<sub>2</sub>PhBr] + Ph<sup>•</sup>
Applications
Oxidative addition and reductive elimination are invoked in many catalytic processes in homogeneous catalysis, e.g., hydrogenations, hydroformylations, hydrosilylations, etc.