Phosphorus–fluorine chemistry. Part XXI. Pentafluorophenylfluorophosphines and pentafluorophenylfluorophosphoranes

Difluorotriorganylphosphoranes for the Synthesis of Fluorophosphonium and Bismuthonium Salts

“…The synthesis and molecular structure of (C 6 F 5 ) 3 PF 2 are well‐known. Although metathetical methods are typically employed for the synthesis of R 3 PF 2 compounds,, the direct fluorination with elemental fluorine and helium as the carrier gas was preferred here [Equation ].…”

Stable Fluorophosphines: Predicted and Realized Ligands for Catalysis

“…[9] The P III ÀF bond is very strong at 545 kJ mol À1 , [10] and metal complexes have been reported for some R 2 PF ligands. [13] Schmutzler, Riesel, and others [13][14][15][16][17] have thoroughly investigated this disproportionation and found that 1) fluorophosphines such as Ph 2 PF, Me 2 PF, and nBu 2 PF disproportionate readily, [13,14] which essentially precludes their application in catalytic processes that involve ligand dissociation; 2) fluorophosphines with bulky or electron-withdrawing substituents such as (C 6 F 5 ) 2 PF, [15] (CF 3 ) 2 PF, [9,16] and tBu 2 PF [17] are thermally stable. [13] Schmutzler, Riesel, and others [13][14][15][16][17] have thoroughly investigated this disproportionation and found that 1) fluorophosphines such as Ph 2 PF, Me 2 PF, and nBu 2 PF disproportionate readily, [13,14] which essentially precludes their application in catalytic processes that involve ligand dissociation; 2) fluorophosphines with bulky or electron-withdrawing substituents such as (C 6 F 5 ) 2 PF, [15] (CF 3 ) 2 PF, [9,16] and tBu 2 PF [17] are thermally stable.…”

“…[11] However, no applications of fluorophosphines in catalysis have been described, [12] perhaps because of the instability of R 2 PF with respect to the disproportionation reaction shown in Equation (1). [13] Schmutzler, Riesel, and others [13][14][15][16][17] have thoroughly investigated this disproportionation and found that 1) fluorophosphines such as Ph 2 PF, Me 2 PF, and nBu 2 PF disproportionate readily, [13,14] which essentially precludes their application in catalytic processes that involve ligand dissociation; 2) fluorophosphines with bulky or electron-withdrawing substituents such as (C 6 F 5 ) 2 PF, [15] (CF 3 ) 2 PF, [9,16] and tBu 2 PF [17] are thermally stable. Whether the source of the stability is thermodynamic or kinetic has not been determined (see below).…”

Stable Fluorophosphines: Predicted and Realized Ligands for Catalysis

“…Schmutzler, Riesel, and others13‐17 have thoroughly investigated this disproportionation and found that 1) fluorophosphines such as Ph 2 PF, Me 2 PF, and n Bu 2 PF disproportionate readily,13, 14 which essentially precludes their application in catalytic processes that involve ligand dissociation; 2) fluorophosphines with bulky or electron‐withdrawing substituents such as (C 6 F 5 ) 2 PF,15 (CF 3 ) 2 PF,9, 16 and t Bu 2 PF17 are thermally stable. Whether the source of the stability is thermodynamic or kinetic has not been determined (see below).…”