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In-Depth Information
SH
OH
SH
OH
HN
O
HN
O
HN
O
HN
O
SH
OH
SH
OH
H
4
-
6
H
4
-
F
[Ti(OPr)
4
]
Na
2
CO
3
methanol
base
M
n+
teranuclear clusters
[M
4
(
F
)
6
]
m
∗
4Ph
4
AsCl
4 Et
4
NBr
S
Ti
S
T
i
(Ph
4
As)
4
S
(Et
4
N)
3
S
S
S
S
S
S
S
S
S
O
N
O
N
O
N
O
O
N
N
O
N
N
N
O
N
N
O
N
O
O
N
O
N
O
S
S
S
S
S
S
Ti
Ti
S
S
S
S
S
S
(Ph
4
As)
4
[Ti
2
(
6
)
3
]
(Et
4
N)
3
[Et
4
NT
2
(
6
)
3
]
=
Scheme 5.3 Reactions of dicatechol and bis(benzene-
o
-dithiol) ligands containing the 1,5-
naphthalenediamido spacer.
{Ti(bdt)
3
}
2
chromophore. The addition of four equivalents of Ph
4
AsCl to the red solu-
tion yielded a deep red precipitate which was identified as the dinuclear complex
(Ph
4
As)
4
[Ti
2
(
6
)
3
]. The formation of the tetrahedral cluster (Ph
4
As)
8
[Ti
4
(
6
)
6
] which had
been obtained under similar reaction conditions with the dicatechol ligand H
4
-
F
[23b]
was not observed. The molecular structure of the tetraanion [Ti
2
(
6
)
3
]
2
is shown in Figure
5.11 (left). The complex anion resides on a crystallographic inversion center located at the
midpoint of the central naphthalene group. Each titanium atom is coordinated by six
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