Abstract
Thioxanthate complexes closely resemble the xanthates and the dithiocarbamates. Like the corresponding xanthates and dithiocarbamates, thioxanthates
of iron(111), nickel(11), and copper(11) are black and those of cobalt(111) are
dark green. In sufficiently dilute
solutions, iron(111) and nickel(11) thioxanthates are
more red than xanthates and dithiocarbamates which
are brownish red. The pressure and temperature dependences of the magnetism
show that the ferric thioxanthates exhibit a
high-spin + low-spin electronic equilibrium, like the ferric dithiocarbamates and xanthates, though the low
spin form predominates for the xanthates and thioxanthates.
Pyridine forms green
paramagnetic adducts in the solid with the nickel(11) complexes which lose
pyridine if left in the open, while in solution a concentration dependent
equilibrium is set up between the planar thioxanthates
and its bis-pyridine adduct. In general the complexes
are rather unstable at room temperature, but some kept fairly well if stored
frozen in sealed tubes. The iron(111) thioxanthates
Fe(S2C-S-R)3 are at least as stable as the corresponding
xanthates. Analogously to the case of the xanthates, the stability of the thioxanthates decreases and the ability of the ligand to
reduce the central metal atom increases with increasing chain length when R is
an alkyl group. Some long-chain ligands are capable of reducing the central iron atom to form
an iron(11) complex. Complexes with branched alkyl chains are more stable than
the straight-chain analogues.
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