An Update on Recent Stoichiometric and Catalytic C–F Bond Cleavage Reactions by Lanthanide and Group 4 Transition-Metal Complexes

Abstract

In organometallic chemistry numerous complexes are known to cleave activated and nonactivated C–F bonds of organic compounds. These reactions are either stoichiometric or catalytic and offer different possibilities for a wide range of synthetic and catalytic applications. This review attempts to summarize a selection of most important developments made since 1997 for C–F bond cleavages by lanthanide and group 4 transition-metal complexes.

Synthesis of Fluorinated Building Blocks by Transition‐Metal‐Mediated Hydrodefluorination Reactions

“…Given the complex mixture of reactive species present in solutions of the “zirconocene” reagent,60 mechanistic details remained unknown. Notably, oxidative addition of fluoroarenes to low‐valent Group 4 metallocenes has several precedents 5a. 61…”

Influence of the Diphosphine Coordinated to Molybdenum and Tungsten Triangular M3S4 Cluster Hydrides in the Catalytic Hydrodefluorination of Pentafluoropyridine

“…In this context, lanthanides and group 4 hydrido complexes have been extensively studied for stoichiometric and catalytic HDF of aromatic, vinylic and aliphatic fluorinated substrates, although the number of catalytic versus stoichiometric transformations is still small [6][7][8][9][10][11][12][13]. Development of a catalytic process implies the challenging conversion of a stable fluorido complex into the corresponding hydrido derivative.…”

Selective CF Bond Activation: Substitution of Unactivated Alkyl Fluorides using YbI3

“…Trivalent lanthanides are known not only to be excellent Lewis acids, but also to form strong bonds to fluorides. [6] As such, it stands to reason that they could potentially be utilized to activate CÀF bonds. The Lewis acidity of lanthanides increases from left to right in the periodic table, with simultaneous decrease in oxophilicity.…”