Pincer-Supported Perfluororhodacyclopentanes: High Nucleophilicity of the M-CF Bond
Shinya Hayashi1, Toshiki Murayama1, Shuhei Kusumoto1
1Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-8656, Japan.
Abstract:
Perfluororhodacyclopentane supported by PBP pincer ligand PBP-RhIII (CF2 )4 (2) was prepared from PBP-RhI -PPh3 (1) and tetrafluoroethylene (TFE). By scXRD analysis, it was revealed that the Rh-CF bond trans to the boryl ligand was largely elongated compared to the one in the apical position. Although M-CF bonds of perfluorometallacyclopentanes are known to be very stable, 2 shows high reactivity toward hydrogenolysis, iodinolysis and protonolysis, thanks to the strong trans-effect of the highly σ-donating boryl ligand. Analogous PCP pincer complex PCP-RhIII (CF2 )4 (4) showed slower reaction rate both in oxidative cyclization with TFE and hydrogenolysis of Rh-CF bond. Catalytic production of 1,1,2,2,3,3,4,4-octafluorobutane from two TFE and hydrogen in one pot was achieved via repetitive oxidative cyclization of TFE and Rh followed by the hydrogenolysis of Rh-CF bonds. This report demonstrates the possible application of PBP-pincer skeleton to the preparation of fluorinated compounds from TFE.
More Related Videos
11:44Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-phosphinetriyltripiperidine]}palladium Under Mild Reaction Conditions
Published on: March 20, 2014
19:58Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
Published on: July 30, 2017
Related Concept Videos
Aromatic Hydrocarbon Anions: Structural Overview
Due to the absence of continuous...
Aromatic Hydrocarbon Cations: Structural Overview
Removing one hydrogen from the intervening CH2 group...
Electrophiles
While a positive electrophile, like a proton, reacts due to its vacant, low-energy 1s orbital, the...
ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH3
Regioselectivity of Electrophilic Additions-Peroxide Effect
Electrophilic Aromatic Substitution: Fluorination and Iodination of Benzene
