Nucleophilic substitution in tris(pentafluorophenyl)phosphine

Abstract

Reaction of tris(pentafluorophenyl)phosphine with various nucleophiles (DMF, HMPA, HEPA, diethylformamide, hydrazine, UDMH, phenylhydrazine, formamide, and aniline) gave exclusively the replacement of all three para fluorines with the exception of aniline, phenylhydrazine, and formamide which gave mixtures of the mono- and bis-4-substituted phosphines. Sodium bisulphide and various alkoxides led mainly to C—P bond rupture though some alkoxides did under certain conditions give some of the expected substitution product. 19F, 31P, and 1H nmr and mass spectral data are presented.

First Solid‐State Structures of Real Diorganyl Phosphinous Acids R2POH (R=CF3, C2F5)

“…For the desired synthesis of (C 2 F 5 ) 2 POH starting from P(C 2 F 5 ) 3 it is necessary to substitute one pentafluoroethyl group by a functional substituent. The cleavage of one PC bond in P(C 6 F 5 ) 3 using alkoxides was reported by Hanna and Miller 11. Wiebe translated this principle into tris(tetrafluoropyridyl)phosphane and generated bis(tetrafluoropyridyl)phosphane oxide 12…”

“…The cleavage of one PÀC bond in PA C H T U N G T R E N N U N G (C 6 F 5 ) 3 using alkoxides was reported by Hanna and Miller. [11] Wiebe translated this principle into tris(tetrafluoropyridyl)phosphane and generated bis-A C H T U N G T R E N N U N G (tetrafluoropyridyl)phosphane oxide. [12] Analogically, an alkaline hydrolysis of PA C H T U N G T R E N N U N G (C 2 F 5 ) 3 with an excess of 1.5 molar aqueous sodium, potassium, or ammonium hydroxide was conducted.…”

19F,31P,1H NMR and X-ray crystallographic studies of (pentafluorophenyl)3−n (4-pyrazol-1-yl-2,3,5,6-tetrafluorophenyl) n=1,2,3 Phosphines

“…Unlike the preceding case mentioned above, nucleophilic reagents like sodium methoxide, methylamine, dimethylformamide, and phen- ylhydrazine afforded exclusively para-substituted (tetrafluorophenyl)phosphines [3,4], whereas the reaction of methylamine with the oxide and sulfide of pentafluorophenyldiphenylphosphine resulted in mixtures of the ortho-and para-substituted compounds [4]. In this paper, we show that a nucleophilic substitution of fluorine atoms in tris(pentafluorophenyl)phosphine, P(C6Fs)3, occurs using pyrazolate anions and leads to para-substituted tetrafluorophenyl groups.…”

Fluoroarylphosphines as ligands

“…Ph 2 P(C 6 F 4 Y-4) Y = OMe, NMeH [34] and P(C 6 F 4 Y-4) 3 Y = NH 2 , NHPh, NMe 2 , NEt 2 , NHNH 2 , NHNMe 2 , NHNHPh, OMe [37] were obtained from Ph 2 P(C 6 F 5 ) and P(C 6 F 5 ) 3 . The reaction between P(C 6 F 5 ) 3 and OP(NMe 2 ) 3 , yielding P(C 6 F 4 NMe 2-4) 3 , was particularly rapid, reaching completion in 10 min.…”

“…Of note is that treatment of the phosphine oxide OPPh 2 (C 6 F 5 ) with MeNH 2 in benzene gave predominantly the ortho-substituted product OPPh 2 (C 6 F 4 NHMe-2), which is presumed to arise from a NHÁ Á ÁO interaction [34]. Treatment of P(C 6 F 5 ) 3 with thiolates lead to P-C bond cleavage [37]. Evidently the nature of the nucleophile is important in determining whether nucleophilic attack occurs at carbon or phosphorus.…”