Mathew, E J; Dr.Mohammed Yusuff,K K(Cochin University of Science & Technology, November , 1990)
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Abstract:
The thesis deals with our studies on the synthesis and
elucidation of structure of some metal complexes of dithio
ligands, such as the dithiocarbamates, xanthates and
2-aminocyclopent-1-ene-1-dithiocarboxylate and its N-alkyl
derivatives.2-Aminocyclopent-1-ene-1-dithiocarboxylate (ACDA) is an
interesting ligand, because of its potential dual capability of
bonding between the metal and the ligand. Since the earlier
reports on the complexes of ACDA contain contradictory ideas on
the nature of its bonding, it was thought worthwhile to undertake
a detailed and systematic study of these type of complexes. As
the ACDA complexes have very low solubilities in solvents like
chloroform, we have used the isopropyl derivative of ACDA as the
ligand. The increased solubility of these complexes have made it
possible to investigate their NMR and solution electronic spectra.The complexes of this ligand have not yet been reported in the
literature.We have synthesised some new mixed ligand complexes of
dithiocarbamates by reacting bis(dithiocarbamato)-µ-dichloro
dicopper complexes (obtained by the reaction of mixed benzoic
dithiocarbamic anhydride and copper(II) chloride) with ACDA or its
N-alkyl derivatives.Interactions of metal halides with the mixed anhydrides
formed from benzoylchloride and xanthates have also been
investigated. Novel complexes of the type, [Cu2(RXant)CI]
(R=i-Bu, i-Pr, n-Bu or n-Pr)) have been isolated from the reaction
of copper(II) chloride and the mixed anhydride, and these
reactions appear to be like the clock reactions reported in the
literature.It also deal with the characterisation of
the complexes of the type [Hg(R2d t c )X] (X=Cl, Br or 1),[Cu3(R2dtc)6][Cu2Br6] and [Cu(R2dtc)Cl2](R2=Me2,Et2,Pip,Morph or Pyrr)respectively, synthesised by simple and novel routes,
different from those reported earlier.
Description:
Department of Applied Chemistry, Cochin
University of Science and Technology