In organometallic chemistry, a migratory insertion is a type of reaction wherein two ligands on a metal complex combine. It is a subset of reactions that very closely resembles the insertion reactions, and both are differentiated by the mechanism that leads to the resulting stereochemistry of the products. However, often the two are used interchangeably because the mechanism is sometimes unknown. Therefore, migratory insertion reactions or insertion reactions, for short, are defined not by the mechanism but by the overall regiochemistry wherein one chemical entity interposes itself into an existing bond of typically a second chemical entity e.g.:
A + B − C ⟶ B − A − C {\displaystyle {\color {red}{\ce {A}}}+{\color {blue}{\ce {B-C}}}\longrightarrow {\color {blue}{\ce {B{-}}}}{\color {red}{\ce {A}}}{\color {blue}{\ce {-C}}}}
Overview
In the migratory insertion, a ligand that is viewed as an anion (X) ligand in and a ligand that is viewed as neutral couple, generating a new anionic ligand. The anion and neutral ligands that react are adjacent. If the precursor complex is coordinatively saturated, migratory insertion often result in a coordinatively unsaturated product. A new (neutral) ligand can then react with the metal leading to a further insertion. The process can occur many times on a single metal, as in olefin polymerization. The anionic ligand can be: H− (hydride), R− (alkyl), acyl, Ar− (aryl), or OR− (alkoxide). The ability of these groups to migrate is called their migratory aptitude. The neutral ligand can be CO, alkene, alkyne, or in some cases, even carbene. Diverse reactions apply to the migratory insertion. One mechanism involves the attack of the anionic ligand on the electrophilic part of the neutral ligand (the anionic ligand migrates to the neutral ligand). The other mechanism involves the neutral ligand that inserts itself between the metal and the anionic ligand.
CO insertion The insertion of carbon monoxide into a metal-carbon bond to form an acyl group is the basis of carbonylation reactions, which provides many commercially useful products. Mechanistic studies reveal that the alkyl group migrates intramolecularly to an adjacent CO ligand.
Early studies were conducted on the conversion of CH3Mn(CO)5 to give the acetyl derivative. Using 13CO, the products is cis [Mn(COCH3)(13CO)(CO)4] (scheme 1).
CO insertion does not always involve migration. Treatment of CpFe(L)(CO)CH3 with 13CO yields a mix of both alkyl migration products and products formed by true insertion of bound carbonyls into the methyl group. Product distribution is influenced by the choice of solvent. Alkyl derivatives of square planar complexes undergo CO insertions particularly readily. Insertion reactions on square planar complexes are of particular interest because of their industrial applications. Since square planar complexes are often coordinatively unsaturated, they are susceptible to formation of 5-coordinate adducts, which undergo migratory insertion readily. In most cases the in-plane migration pathway is preferred, but, unlike the nucleophilic pathway, is inhibited by an excess of CO.
Effects on reaction rates Steric effects strain – Increasing the steric strain of the chelate backbone in square planar complexes pushes the carbonyl and methyl groups closer together, increasing the reactivity of insertion reactions. Oxidation state – Oxidation of the metal tends to increase insertion reaction rates. The main rate-limiting step in the mechanism is the migration of the methyl group onto a carbonyl ligand, oxidizing the metal by imparting a greater partial positive charge on the acetyl carbon, and thus increasing the rate of reaction. Lewis acids – Lewis acids also increase the reaction rates, for reasons similar to metal oxidation increasing the positive charge on the carbon. Lewis acids bind to the CO oxygen and remove charge, increasing the electrophilicity of the carbon. This can increase the reaction rate by a factor of up to 108, and the complex formed is stable enough that the reaction proceeds even without additional CO to bind to the metal. Electronegativity of the leaving group - Increasing the electronegativity of the leaving alkyl group stabilizes the metal-carbon bond interaction and thus increases the activation energy required for migration, decreasing the reaction rate. Trans-effect – Ligands in an octahedral or square planar complex are known to influence the reactivity of the group to which they are trans. This ligand influence is often referred to as the trans-influence, and it varies in intensity between ligands. A partial list of trans-influencing ligands is as follows, from highest trans-effect to lowest: aryl, alkyl > NR3 > PR3 > AsR3 > CO > Cl. Ligands with a greater trans-influence impart greater electrophilicity to the active site. Increasing the electrophilicity of the CO group has been shown experimentally to greatly increase the reaction rate, while decreasing the electrophilicity of the methyl group slightly increases the reaction rate. This can be demonstrated by reacting a square planar [(PN)M(CO)(CH3)] complex with CO, where PN is a bidentate phosphorus- or nitrogen-bound ligand. This reaction proceeds in much greater yield when the methyl group is trans-P and the CO trans-N, owing to the higher trans-influence of the more electronegative nitrogen.
Reverse reaction Decarbonylation of aldehydes, the reverse of CO insertion, is a well-recognized reaction:
RCHO → RH + CO The reaction is not widely practiced in part because the alkanes are less useful materials than are the aldehyde precursors. Furthermore, the reaction is not often conducted catalytically because the extruded CO can be slow to dissociate. Extrusion of CO from an organic aldehyde is most famously demonstrated using Wilkinson's catalyst:
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