SYNTHETIC AND SPECTROSCOPIC STUDIES OF SOME ORGANOTIN COMPOUNDS
SYNTHETIC AND SPECTROSCOPIC STUDIES OF SOME ORGANOTIN COMPOUNDS
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Date
1982-06
Authors
BONIRE, JOSIAH JIMOH
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Abstract
In this work, hitherto unreported 4-acetylpyridine
and 4-benzoylpyridine adducts of Me3SnCl are synthesized.
The adducts are found to be 1:1 Lewis acid: bases,
3-Acetyl-, 3-benzoyl-, 4-acetyl-, and 4-benzoyl pyridine
adducts, 1:2 Lewis acid: bases, of Me2nCl2, MeSnCl3,
SnCl4, PhSnCl3, and Ph2SnCL2, are also synthesized.
Infrared spectroscopy shows that only the N binding
site of the Lewis bases forms the coordinate bond in adduct
formation.
For the 1:1 2-benzoylpyridine adducts of MeSnCl3,
SnCl4, and PhSnCl3, i.r. shows that both N and 0 binding
sites of the Lewis base coordinate.
I.r. spectroscopy also indicates that for the 1:1
2-pyridine carboxaldehyde adduct of PhSnCl3, both N and 0
binding sites of the Lewis base coordinate. 2-Acetylpyridine
reacts in a manner different from 2-benzoylpyridine
and 2-pyridine carboxaldehyde, with the methyltin, phenyltin,
and stannic chlorides. The exact nature of the reactions
is yet to be worked out.
Proton magnetic spectra of the pyridine adducts of
the methyltin, phenyltin, and stannic chlorides are
presented perhaps for the first time. P.m.r. specra of
the new adducts synthesized were also run. P.m.r.
chemical shifts of the adducts provide another way of
showing Lewis base coordination.
The JSn-C-H values for methyltin chloride adducts of
pyridine Lewis bases are found to be almost linearly
related to the pV, of the Lewis bases, and could thus be
used to correlate the base strength of Lewis bases,
especially of a Lewis base and its substituted derivatives,
where the substituents do not sterically interfere
with the freedom of the Lewis base to bind with a Lewis
acid.
Investigation of the substitution reactions of the
organotin halide adducts was undertaken. Some methyltin
trifluoroacetate adducts were synthesized. Ph3SnO.CO.CF3
is made by a simpler, more efficient method than previously
reported.
By its mode of reaction, PhSn(O.CO.CF3)2 might serve
as a new radical initiator.
Through photolysis or thermal decomposition,
diphenyltin bis-trifluoroacetate undergoes an unusual
disproportionation reaction, yielding biphenyl and a
complex dimer of the phenyltin bis-trifloroacetate radical.
Description
A THESIS SUBMITTED TO THE POSTGRADUATE SCHOOL, AHMADU
BELLO UNIVERSITY, IN FULFILLMENT OF THE REQUIREMENT
FOR THE DEGREE OF DOCTOR OF PHILOSOPHY IN CHEMISTRY.
Department of Chemistry,
Faculty of Science,
Ahmadu Bello University,
Zaria.
Keywords
SYNTHETIC,, SPECTROSCOPIC STUDIES,, ORGANOTIN COMPOUNDS,