Migratorische Insertion von Alkenen in Metall‐Sauerstoff‐ und Metall‐Stickstoff‐Bindungen

Abstract

Die Insertion ungesättigter Liganden in M‐C‐ oder M‐H‐Bindungen verläuft über eine migratorische Insertion, die eine fundamentale metallorganische Reaktion ist. Jüngste Berichte bestätigen migratorische Insertionen von Alkenen in M‐O‐ und M‐N‐Bindungen im Verlauf von Alkenalkoxylierungen bzw. Alkenaminierungen. Wir geben hier einen Überblick über den Stand der Literatur und wollen außerdem betrachten, wie diese jüngsten Studien mit klassischen Experimenten der Bildung von C‐O‐ und C‐N‐Bindungen mit Alkenkomplexen später Übergangsmetalle zusammenhängen.

Olefin Insertion into a Pd–F Bond: Catalyst Reactivation Following β‐F Elimination in Ethylene/Vinyl Fluoride Copolymerization

“…[3] Insertions of styrenes and alkynes into Pd À Fb onds were proposed as key steps in the Pd-catalyzed aminofluorination and fluoroesterification of styrenes and fluorination/cyclization of enynes. [4][5][6] IrÀFa nd PtÀFc omplexes react with CS 2 to generate fluoro-dithiocarbonato species,and computational and experimental studies support aconcerted insertion mechanism in the former case. [7] Herein we report adiscrete Pd fluoride complex that inserts ethylene and vinyl fluoride and show that these reactions have important consequences in the Pd-catalyzed copolymerization of these monomers.…”

“…Right:Molecular structure of 7. [35] Hatoms and aCH 2 Cl 2 molecule are omitted; ellipsoids are set at 50 %probability.Selected bond lengths []: Pd1-C1 2.045(2), Pd1-O1 2.1277(15), Pd1-N1 2.1337(18), Pd1-P1 2.2459- (6).…”

“…(SIPr)AuF reacts with internal alkynes to yield trans addition products via nucleophilic attack of F À on an intermediate Au alkyne complex. [4][5][6] IrÀFa nd PtÀFc omplexes react with CS 2 to generate fluoro-dithiocarbonato species,and computational and experimental studies support aconcerted insertion mechanism in the former case. [4][5][6] IrÀFa nd PtÀFc omplexes react with CS 2 to generate fluoro-dithiocarbonato species,and computational and experimental studies support aconcerted insertion mechanism in the former case.…”

Palladium(II)‐Catalyzed Cope‐Type Hydroamination: Efficient Access to Five and Six‐Membered Cyclic Nitrones

“…al. [18,19] The use of more nucleophilic oxime as the nitrogen source for direct aminopalladation has rarely been documented. A comparison across the different types of substrates surveyed in this study indicate the following order of reactivity: 2 > 4, 5, 6 > 7 @ 8, with a trend of increasing nucleophilicity of the nitrogen, suggesting that more coordinating nitrogen centers can possibly inhibit catalysis by strongly bonding to Pd(II) center.…”