Zirconocene Dichloride Catalyzed Hydrodefluorination of CF bonds

Abstract

A two-metal job: Four-coordinate aluminum dihydrides such as 1 are reported as terminal reductants for the selective title reaction. The heterobimetallic complex 2 has been isolated and shown to be catalytically competent.

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.…”

Activation and Formation of Aromatic C–F Bonds

“…31) [64]. The yields and substrate scope were significantly increased when four-coordinate diketiminatestabilized aluminum hydrides were used as reductants.…”

Aromatic C–F Bond Activation by Rare-Earth-Metal Complexes

“…[15][16][17][18][19][20][21][22] Albeit in most cases C-F bond activation was achieved in a stoichiometric fashion due to the high stability of the corresponding metal fluoride, a common product of metal mediated C-F bond transformations, it is possible to make the reaction catalytic through the use of a fluorine trapper such as a silane or aluminum hydride by taking advantage of the strength of the Si-F and Al-F bonds. [23][24][25][26][27] Scheme 1. Representative examples of C-F bond activation by rare-earth metal complexes: (a) Reaction of Cp*2Yb(II) (Cp* = η 5 -C5Me5) with perfluorobenzene; 36 (b) Activation of fluorocarbons by Cp'2CeH (Cp' = η 5 -C5H2(CMe3)3-1,2,4); 37-38 (c) F/I exchange between alkyl fluorides and YbI3.…”