cine andtele Nucleophilic Substitutions in (η6-Arene)tricarbonylchromium and Tricarbonyl(η5-cyclohexadienyl)manganese Complexes

Abstract

Addition of a nucleophile to an (η6‐arene)tricarbonylchromium or a tricarbonyl(η5‐cyclohexadienyl)manganese complex substituted with a leaving group X (X = F, Cl, OMe, OPh, NR2) affords (after treatment with acid) new complexes with the same η6 or η5 hapticity. The overall reaction involves addition of the nucleophile ortho, meta, or para with respect to the leaving group and HX elimination. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

The coordination chemistry of organo-hydride donors: new prospects for efficient multi-electron reduction

“…The synthesis of these compounds is classic, textbook organometallic chemistry; [249][250][251] a number of reviews have also been published. [252][253][254][255][256][257] Some examples of conversion of p-benzene metal complexes to a cyclohexadienyl anion complex are documented below, and are sufficient to illustrate the potential scope of non-heterocyclic ligands as hydride carriers.…”

Lithiation/Electrophilic Quench of [(η5‐Cyclohexadienyl)Mn(CO)3]: Versatile Functionalization and Resolution of Planar Chirality in the Organomanganese Series

“…The first cine and tele nucleophilic substitutions of [(η 5 ‐cyclohexadienyl)Mn(CO) 3 ] complexes were developed in 1996 by treatment with hydrides and a proton source,5 and their mechanism was shown to be very close to the cine and tele aromatic nucleophilic substitution (SN Ar ) described for [(η 6 ‐arene)Cr(CO) 3 ] complexes 3d. The discovery of Pd cross‐coupling reactions in the η 5 ‐cyclohexadienyl–Mn series6 enabled ready access to a large variety of substituted η 5 complexes bearing double or triple bonds, aryl, or keto groups linked to the π system.…”

Chromium arene complexes in organic synthesis

“…There are a couple of excellent reviews that cover this chemistry comprehensively so we will summarize the main aspects and give an account of the most recent work. 26 In a typical reaction, 2-lithio-1,3-dithiane reacts with benzene chromium tricarbonyl to give an anionic g 5 -cyclohexadienyl complex 76. This intermediate has been characterized by X-ray diffraction analysis by Semmelhack et al 27 Oxidation of 76 with of I 2 gives the substituted arene 77 (Scheme 22).…”