Synthesis and Chemistry of Perfluoroalkylphosphines.

UoM administered thesis: Phd

  • Authors:
  • Farouk Al'Issa

Abstract

The synthesis of new perfluoroalkyl-containing phosphines from the reactions of the perfluoroalkyl iodides n-C3F7I, i-C3F7I, n-C4F9I, sec-C4F9I, cyc-C6F11Br or cyc-C6F11I, n-C6F13I and n-C8F17I with R2PSiMe3 or R2PLi (R = Ph2, t-Bu2, Et2, MePh and EtPh was investigated. The new perfluoroalkyl-containing phosphines were characterised by multinuclear NMR spectroscopy. The reaction between i-Pr2P-Pi-Pr2 and i-C3F7I resulted in some i-Pr2PCF(CF3)2, 11, but an elimination process was dominant. Compound 11 was obtained using a reaction of i-Pr2PCl with i-C3F7I in the presence of MePh2P, dpph, dppm, dppe or dppp. This method was also applied successfully to other systems.The reaction of PhPLi2 with n-C3F7I has been investigated, but does not result in production of a bis-perfluoroalkyl-containing phosphine, instead the previously unknown compound, PhHP(CF2)2CF3, 21, was formed.The chemistry of the perfluoroalkyl-containing phosphines has been investigated; oxides of the perfluoroalkyl-containing phosphines were made by either aerial oxidation, or by adding hydrogen peroxide solution. Oxidation with XeF2 was also investigated, to give compounds of the type F2PPh2Rf. These were water sensitive and also generated phosphine oxides. The phosphorus(V) selenides have been synthesised, and their 1J(PSe) coupling constants measured.The coordination chemistry of the perfluoroalkyl-containing phosphines was investigated and complexes of rhodium, molybdenum, gold, platinum and palladium were prepared. The crystal structures of six of these complexes have been obtained, they are: RhCl(CO)[Ph2P(CF2)2CF3]2, RhCl(CO)[Ph2P(C6F11)]2, RhCl(CO)[Ph2PCF(CF3)2]2, trans-[PdCl2(Ph2P(CF2)2CF3)2], cis-[PtCl2(Ph2P(CF2)2CF3)2] and trans-[PtCl2(Ph2P(CF2)5CF3)2]. In all of these structures aggregation of the fluorinated alkyl groups occur with F...F distances of ca. 2.8 A, resulting in fluorous domains being observed.

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Original languageEnglish
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Award date1 Aug 2019