Transition Metal Arene π-Complexes in Organic Synthesis and Catalysis

Synthesis and structure of tricarbonyl(η6-arene)chromium complexes of phenyl and benzyl D-glycopyranosides

“…In general, tricarbonyl(η 6 -arene)chromium compounds can be prepared in a wide variety of methods [4]. However, the following two methods are the most commonly employed ones: (a) ligand-exchange reaction between an arene and, most conveniently, either naphthalene–Cr(CO) 3 complex or (MeCN) 3 Cr(CO) 3 in which the chromium ligand is only weakly bound [14]; (b) simply heating the arene with hexacarbonylchromium in an inert solvent (Mahaffy–Pauson method) [15–16].…”

“…Since then, a plethora of transition-metal complexes of arenes have been prepared, characterized and described in the literature. Among the multitude of transition-metal complexes of aromatic compounds, however, only tricarbonyl(η 6 -arene)chromium compounds are widely used for organic syntheses [2–4]. This is due to the fact that tricarbonyl(η 6 -arene)chromium complexes are relatively stable compounds, which can be easily prepared and also easily reconverted into the parent arenes.…”

Transition-Metal-Catalyzed Dehydrogenative (3 + 2) Annulation of Aromatic Compounds: Synthesis of Indenes and Indanes via Dual Functionalization of Benzylic and ortho C–H Bonds

“…Electrophilic transition metal units, such as [Cr­(CO) 3 ] and [CpRu] + , were found to activate alkylarenes through π-coordination to their aromatic rings, leading to enhanced reactivity toward benzylic deprotonation . Such reactivity of transition-metal η 6 -arene complexes has been extensively studied, and a large array of reactions of benzylic C–H bonds, including addition to electrophiles, palladium-catalyzed cross-coupling, and H/D exchange, that would not easily take place on unbound arenes has been reported to date .…”

Topology-Dependent Synthesis, Structures, and Bonding Interactions of Uranium Polyarene Complexes

“…Since Fischer and Hafner’s landmark work on bis­(benzene)­chromium, metal arene complexes have grown into an important class of organometallic compounds. , The unique metal–arene interactions have motivated the advancement of chemical bond theory, , and enabled a wide range of applications in synthesis and catalysis, − as well as materials sciences − and medicine. , In addition, ligand designs incorporating metal–arene interactions led to breakthroughs in stabilizing unusual oxidation states, − and empowered small molecule activation and catalysis. − Polyarenes have been extensively studied as organic semiconductors, because of their synthetic tailorability and peculiar photochemical and electrochemical properties. − Based on the topology, polyarenes can be classified into two subgroups, linear polyarenes (acenes) and nonlinear polyarenes (Figure a) . Recently, metal polyarene complexes have attracted considerable attention, due to their intriguing electronic structures, synthetic flexibility, and tunable structures and properties, ,,, as well as potential applications in metal-ion batteries. , Moreover, they may serve as models for studying the behaviors and effects of metal ions on carbon π-surfaces, such as graphene and fullerene. , …”