FT-IR and MAS NMR analysis of montmorillonite K10 supported MF2 reagents and their activity as catalysis /

ZnF2, CdF2, and CUF2 have been adsorbed onto the surface of montmorillonite K10, and the infrared and 19F, 27 AI, and 29Si MAS NMR spectra of the reagents over a range of loadings have been obtained. CUF2 was observed to attack the Si02 layer and form the complex CuSiF6, Zn F2 tends to attack the aluminium oxide layer, in which Zn isomorphously replaces AI, and forms AIF3 and AIF4 - complexes. All the spectroscopic evidence ruled out the formation of any AI-F and/or Si-F free species as CdF2 is adsorbed on the surface of montmorillonite K10. The reactivity of MF2-K10 reagents towards Friedel-Crafts benzylation of benzene with benzyl chloride varied from one reagent to another. ZnF2-K10 was observed to be the most reactive and CUF2 was the least reactive.

On the Ewald method and the quartic Helmholtz free energy of an anharmonic metallic crystal

Thesis (M. Sc.) - Brock University, 1978.

Pressure dependence of spin fluctuations in metallic glasses Zrâ â Niâ â ,Zrâ â (Nix/Feâ â â -x)â â and /Zrx/feâ â â -x

The superconducting transition temperature Tc of metallic glasses ZrxFelOO-x (x=80, 75), Zr75(NixFelOO-x)25 (x=75, 50, 25), and CU2SZr75 were measured under quasi-hydrostatic pressure up to 8 OPa (80kbar). The volume (pressure) dependence of the electron-phonon coupling parameters Aep for CU25Zr75 was calculated using the McMillan equatio11. Using this volume dependence of Aep and the modified McMillan equation which incorporates spin-fluctuations, the volume dependence of the spin fluctuation parameter, Asf, was determined in Zr75Ni25, ZrxFelOO-x , a11d Zr75(NixFelOO-x)25. It was found that with increasing pressure, spinfluctuations are suppressed at a faster rate in ZrxFe lOO-x and Zr75(NixFelOO-x)25, as Fe concentration is increased. The rate of suppression of spin-fluctuations with pressure was also found to be higher in Fe-Zr glasses than in Ni-Zr glasses of similar composition.

Studies of nucleophilic attack on tris (pentafluorophenyl) phosphine and its oxides

The reaction of tris(pentafluorophenyl)phosphine [5] with the nucleophiles dimethyl formamide (DMF), hexamethylphosphoric triamide (HMPA), diethyl formamide (DEF), hexaethylphosphoric triamide (HEPA), hydrazine, N,N-dimethyl hydrazine (in presence and/or absence of KF), phenylhydrazine, ammonium hydroxide, formamide, aniline, sodium hydrogen sulfide, and hexaethylphosphorous triamide was investigated. The reaction of [5] with DMF and HMPA gave the same product, namely tris-[4-(N,N-dimethylamino)-2,3,5,6-tetrafluorophenyl]phosphine [12] but in higher yield in the case of HMPA. Compound (5] also reacted with DEF to give tris[4-(N,N-diethylamino)-2,3,5,6-tetrafluorophenyl] phosphine [14]. When [51 was treated with HEPA, it gave a mixture of bis(pentafluorophe~yl)-(N,N-diethylamino-tetrafluorophenyl)phosphine, pentafluorophenyl-bis-(N,N-diethylamino-tetrafluorophenyl)phosphine and tris (N,N-diethylamino-tetrafluorophenyl)phosphine. Treatment of [5] with aqueeus hydrazine solution in excess ethanol gave tris(4-hydrazo-2,3,4,6-tetrafluorophenyl)phosphine [1s1 in high yield while reaction with aqueous hydrazine led to C-P cleavage and production of tetrafluorophenyl hydrazine. With N,N-dimethyl hydrazine, [5] gave tris(4-N,N-dimethylhydrazine-2,3,5,6-tetrafluorophenyl) phosphine {20j. The latter could be obtained in higher yield and shorter reaction time, by the addition of KF. The reaction of compound {51 with phenylhydrazine in THF gave bis(pentafluorophe~yl)-4-S-phenylhydrazino- 2,3,5,6-tetrafluorophenyl phosphine [22] in low yield. Reaction of [5] with ammonium hydroxide in THF at high pressure in the presence of KF gave tris-~4-amino-2,3,5,6-tetrafluorophenyl)phosphine [25]. Similarly, formamide led to a mixture of (C6F4NHZ)3P, (C6F4NHZ)ZPC6FS, (C6F4NHZ)ZPC6F4NHCHO, and C6F4NHZP(C6Fs)(C6F4NHCHO). When [5] was treated with aniline, a mixture of mono-, di-, and tri-substituted products was obtained. Sodium hydrogen sulfide in ethylene glycol/ pyridine led to C-P cleavage and the isolation of pentafluorobenzene and tetrafluorothiophenol. Reaction of [5] and its oxide [35] with different alkoxides in the corresponding alcohols led mainly to C-P bond cleavage products, with the exception of one case where sodium methoxide was used in ether, and which led to tris-(4-methoxy-2,3,9,6-tetrafluorophenyl)phosphine [37]. On the basis of various spectroscopic data, it was concluded that the para position in compound [5] was generally the favoured site of attack.