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Molecular structure of the anion [TiCp(14)]
.
Figure 5.5
backbone, the
endo
bend is larger than the
exo
bend. An inverse situation has been
observed in the related anion [Ti(Cp)(bdt)
2
]
with two unbridged benzene-
o
-dithiolato
ligands [33].
Mononuclear chelate complexes have also been obtained from the tris(benzene-
o
-
dithiola) ligand H
6
-
8
and metal ions that are capable of coordinating three benzene-
o
-
dithiolato units [27]. Ligand H
6
-
7
with a shorter linker between the donor groups and the
central phenylene moiety, however, does not yield a mononuclear complex but reacts with
octahedrally coordinated metal centers under the formation of a tetranuclear cluster of
type [M
IV
4
(
7
)
4
]
8
(see below). Complex (Ph
4
As)
2
[Ti(
8
)] was obtained from the reaction
of equimolar amounts of H
6
-
8
and [Ti(OPr)
4
] in the presence of an excess of Li
2
CO
3
followed by cation exchange with Ph
4
AsCl [27]. Figure 5.6 shows the molecular structure
of the complex anion [Ti(
8
)]
2
. The metal center is sourrounded by the six sulfur donors
in a distorted octahedral fashion similar to the geometry observed for the metal complexes
of related tri(catecholato) ligands [34,35]. The orientation of the amide groups indicated
the presence of intramolecular N
H
S hydrogen bonds which probably have a
Figure 5.6 Molecular structure of the complex anion [Ti(8)]
2
.
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