Regioselective carbon-fluorine bond cleavage reactions from the interaction of transition metal fluorocarbon complexes with nucleophiles

Fluoroarylphosphines as ligands

“…A similar reaction was observed with NaNH 2 [131]. All four ortho fluorine atoms were substituted by treatment of the salt 5 (X = ClO 4 À or CF 3 SO 3 À ) with five equivalents of NaOMe.…”

“…Treatment of trans-[PtMe(THF){PPh 2 (C 6 F 5 )} 2 ]X (5) with aqueous KOH rapidly afforded the metallacyclic complex [PtMe(kP,kO-Ph 2 PC 6 F 4 O-2){PPh 2 (C 6 F 5 )}], the identity of which was confirmed by a structure determination by singlecrystal X-ray diffraction, in 68% yield [130,131]. A similar reaction was observed with NaNH 2 [131].…”

“…The reaction was rapid and afforded trans-[Pt(OMe)Me(PPh 2 {C 6-F 3 (OMe) 2 -2,6}) 2 ] in quantitative yield. Although the intramolecular nature of the reaction was not confirmed ortho substitution strongly suggests an intramolecular nucleophilic reaction for which the mechanism depicted in Scheme 11 has been proposed [131].…”

Methyl(2-phosphanylphenolato[P,O])nickel(II) Complexes – Synthesis, Structure, and Activity as Ethene Oligomerization Catalysts

“…This can be mainly attributed to the more facile dissociation of PMe 3 from 2e. (10); P1-C1-C2 118.7(8), P1-C1-C6 122.1 (8), O1-C2-C1 119.9(9), O1-C2-C3 116.9 (10) When the reaction was carried out in the presence of one equivalent of PMe 3 , 2e was isolated (Scheme 2). The complexes 2 were purified by fractional extraction of the crude products with pentane.…”

“…Exceptions are complexes with PMe 3 and PPhMe 2 ligands, which give α-olefins of low molecular weight (C 4ϭ to C 24ϭ ), although with lower catalytic activity. [3d] In view of the recently reported access to variously substituted 2-phosphanylphenols [8,9] and their high tendency to form P ʝ Ochelates, [8,10,11] we turned our attention to the synthesis of catalytically active (2-phosphanylphenolato [P,O])nickel(II) complexes and the tuning of their activity and selectivity by variation of substituents at the phosphorus and the phenolate group. We report here on methyl(2-phosphanylphenolato)nickel complexes, which differ from cyclopentadienyl(2-phosphanylphenolato)nickel(II) complexes [8b,11] in that they are active oligomerization catalysts.…”