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Concept
Transmétallation
Résumé
Transmetalation (alt. spelling: transmetallation) is a type of organometallic reaction that involves the transfer of ligands from one metal to another. It has the general form:
M1–R + M2–R′ → M1–R′ + M2–R
where R and R′ can be, but are not limited to, an alkyl, aryl, alkynyl, allyl, halogen, or pseudohalogen group. The reaction is usually an irreversible process due to thermodynamic and kinetic reasons. Thermodynamics will favor the reaction based on the electronegativities of the metals and kinetics will favor the reaction if there are empty orbitals on both metals. There are different types of transmetalation including redox-transmetalation and redox-transmetalation/ligand exchange. During transmetalation the metal-carbon bond is activated, leading to the formation of new metal-carbon bonds. Transmetalation is commonly used in catalysis, synthesis of main group complexes, and synthesis of transition metal complexes.
There are two main types of transmetalation, redox-transmetalation (RT) and redox-transmetalation/ligand-exchange (RTLE). Below, M1 is usually a 4d or 5d transition metal and M2 is usually a main group or 3d transition metal. By looking at the electronegativities of the metals and ligands, one can predict whether the RT or RTLE reaction will proceed and what products the reaction will yield. For example, one can predict that the addition of 3 HgPh2 to 2 Al will yield 3 Hg and 2 AlPh3 because Hg is a more electronegative element than Al.
M1n+–R + M2 → M1 + M2n+–R.
In redox-transmetalation a ligand is transferred from one metal to the other through an intermolecular mechanism. During the reaction one of the metal centers is oxidized and the other is reduced. The electronegativities of the metals and ligands is what causes the reaction to go forward. If M1 is more electronegative than M2, it is thermodynamically favorable for the R group to coordinate to the less electronegative M2.
M1–R + M2–X → M1–X + M2–R.
In redox-transmetalation/ligand exchange the ligands of two metal complexes switch places with each other, bonding with the other metal center.
Source officielle
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