<p> A continuation of studies of main group compounds
carried out in this laboratory has led to the investigation
of the structural and oxidative chemistry of several
compounds and mixtures of the elements phosphorus, arsenic,
sulfur and selenium. A number of questions and a lack of
data regarding known compounds of these elements lead to
an examination of the series P4-X^AsX^S3-Y^SeY, X = 0-4,
Y = 0-3. Raman spectra of several members of the series
have been recorded. The 31P and natural abundance 77Se
nmr spectra of these compounds were also recorded, including
a reinvestigation and complete assignment of the 31P nmr
spectrum of P4Se3 . Several trends in the coupling constants
and chemical shifts were noted and an empirical equation
was devised for the 31P nmr spectral assignments for
quaternary members of the series. The compound formerly
believed to be P2As2S3 was shown to be PAs3S3. The crystal structure of an occupationally disordered crystal
of stoichiometry P2As2S3 is also reported in this thesis.</p> <p> The compound As4S4 and 1:1 As:Se fused mixtures
were separately oxidized with the Lewis acids AsF5 and
SbF5 to produce the new cations As3S4+ and As3Se4+. The cations were characterized as the salts As3S4 (AsF6), As3S4 (SbF6), As3Se4 (AsF6 ) and As3Se4 (SbF6) by Raman spectroscopy and infrared spectroscopy. The determination of the crystal structures of the first three salts is also reported.</p> <p> Reactions of As4S4 with PF5, PCl5, BCl3, SO3, NbF5 , TaF5 and WF6 were shown to not proceed or, in the case of
PF5, to not produce a stable adduct. The action of AsF5
on compounds and mixtures of heavy main group elements
(e.g., Sb2Te3) of groups V and VI produced no new compounds
that were identified and generally just gave known homo-polyatomic cations of the chalcogens.</p> <p> Oxidation of As4S4 with the halogens (X) chlorine and bromine produced AsX3 and S2X2 while the reaction of SbCl5 with As4S4 or 1:1 As:Se fused mixtures produced SbCl3, AsCl3 and the salts SCl3 (SbCl6) and SeCl3 (SbCl6),respectively. The crystal structure of SCl3 (SbCl6) is reported here along with unit cell data for SeCl3 (SbCl6) and SBr1.2Cl1.8 (SbCl6) and the Raman data for all three compounds. Only AsSI was produced by the oxidation of
As4S4 by I2 in SO2 while a reaction between molten P4Se3
and I2 gave the new compound αP4Se3I2. Raman spectra for both AsSI and αP4Se3I2 were recorded as well as the 31P nmr spectrum for the latter.</p> / Thesis / Doctor of Philosophy (PhD)
| Identifer | oai:union.ndltd.org:mcmaster.ca/oai:macsphere.mcmaster.ca:11375/17461 |
| Date | 07 1900 |
| Creators | Christian, Beverley Howard |
| Contributors | Gillespie, R.J., Chemistry |
| Source Sets | McMaster University |
| Language | en_US |
| Detected Language | English |
| Type | Thesis |
Page generated in 0.0012 seconds