Mechanism of the Iridium-Catalyzed Silylation of Aromatic C–H Bonds

<p>The iridium-catalyzed silylation of aromatic C–H bonds has become a synthetically valuable reaction because it forms aryl silanes with high sterically derived regioselectivity with silane reagents that are produced and consumed on large scales. Many groups, including our own, have reported iridium complexes of phenanthroline or bipyridine ligands as catalysts for this reaction. Yet, little is known about the mechanism by which the iridium-catalyzed silylation of arenes occurs. Indeed, no iridium-silyl complexes have been prepared that react with C-H bonds to form C-Si bonds in a fashion that is chemically and kinetically competent to be part of the catalytic cycle. </p><p><br></p> <p>In this manuscript, we report the synthesis and reactivity of iridium-silyl compelexes of the 2,9-Me₂Phen ligand that generates the most active known catalyst for the silylation of aromatic C-H bonds. We show by experiment and computation that the most stable and most reactive silyl complex of this ligand contains two silyl and one hydride ligands and by kinetic analysis of the catalytic reaction determine the rate-limiting step for arenes with varying electronic properties. Computational studies indicate that the steric encumberance of the phenanthroline ligand controls the number of silyl ligands bound to iridium and that the difference in the number of silyl ligands leads to large differences to the rates of the reaction. These studies provide insight into the origins of the high activity of the catalyst containing the 2,9-Me₂Phen ligand.</p>

Mechanism of the Iridium-Catalyzed Silylation of Aromatic C–H Bonds

<p>The iridium-catalyzed silylation of aromatic C–H bonds has become a synthetically valuable reaction because it forms aryl silanes with high sterically derived regioselectivity with silane reagents that are produced and consumed on large scales. Many groups, including our own, have reported iridium complexes of phenanthroline or bipyridine ligands as catalysts for this reaction. Yet, little is known about the mechanism by which the iridium-catalyzed silylation of arenes occurs. Indeed, no iridium-silyl complexes have been prepared that react with C-H bonds to form C-Si bonds in a fashion that is chemically and kinetically competent to be part of the catalytic cycle. </p><p><br></p> <p>In this manuscript, we report the synthesis and reactivity of iridium-silyl compelexes of the 2,9-Me₂Phen ligand that generates the most active known catalyst for the silylation of aromatic C-H bonds. We show by experiment and computation that the most stable and most reactive silyl complex of this ligand contains two silyl and one hydride ligands and by kinetic analysis of the catalytic reaction determine the rate-limiting step for arenes with varying electronic properties. Computational studies indicate that the steric encumberance of the phenanthroline ligand controls the number of silyl ligands bound to iridium and that the difference in the number of silyl ligands leads to large differences to the rates of the reaction. These studies provide insight into the origins of the high activity of the catalyst containing the 2,9-Me₂Phen ligand.</p>

Synthesis and structures of anionic rhenium polyhydride complexes of boron–hydride ligands and their application in catalysis

Exhaustive deoxygenation of perrhenate by pinacol borane forms a new Re anion of boron and hydride ligands only that undergoes borane ligand exchange, stoichiometric C–H boration, and catalytic pyridine hydroboration.

Kinetic stabilization of low-oxidation state and terminal hydrido main group metal complexes by a sterically demanding N,N′-bis(2,6-terphenyl)triazenide

Thermally robust main group metal complexes featuring terminal hydride ligands are achieved by deploying a sterically demanding N,N′-bis(2,6-terphenyl)triazenide ligand.

Ab initio accelerated molecular dynamics study of the hydride ligands in the ruthenium complex: Ru(H2)2H2(P(C5H9)3)2

The dihydrogen complex Ru(H2)2H2(P(C5H9)3)2 has been investigated, via ab initio accelerated molecular dynamics, to elucidate the H ligands dynamics and possible reaction paths for H2/H exchange.