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Li
x
Na
4-x
OH
O
Ti
OH
O
O
N
H
O
N
H
[TiO(acac)
2
]+
[MoCl
4
(CH
3
CN)
2
]
Li
2
CO
3
/Na
2
CO
3
MeOH / DMF
O
N
H
O
N
H
SH
S
Mo
SH
S
3
H
4
-
13
(Li
x
Na
4-x
)[TiMo(
13
)
3
]
4 (PNP)Cl
DMF / Et
2
O
2 (PNP)Cl
MeOH / Et
2
O
(PNP)
4
Li
1.5
Na
0.5
(PNP)
2
O
O
Ti
Ti
O
O
H
O
N
O
N
H
O
N
H
O
N
H
S
S
Mo
Mo
S
S
3
3
(PNP)
4
[TiMo(
13
)
3
]
Li
1.5
Na
0.5
(PNP)
2
[TiMo(
13
)
3
]
Scheme 5.6 Synthesis of
the heterobimetallic helicates
(PNP)
4
[TiMo(13)
3
]and
Li
1.5
Na
0.5
(PNP)
2
[TiMo(13)
3
].
Transmetallation of supramolecular structures obtained by classical or subcomponent
assembly constitutes a promising strategy to overcome these shortcomings. For example,
supramolecular structures containing ligands not accessible by conventional organic syn-
thesis could be obtained by subcomponent self-assembly, and transmetallation would sub-
sequently allow the use of these ligands in classical supramolecular chemistry.
We studied the incorporation of the sulfur donor function into Schiff base ligands. In
contrast to most Schiff bases, the thiosalicylaldimine (
o
-mercaptobenzaldimine, NS) subunit
is not accessible by direct condensation of an amine with the corresponding
o
-mercaptoben-
zaldehyde, which instead leads to 1,5-dithiocins [53,54]. However, treatment of a preformed
complex bearing a 2-thiolatobenzaldehyde ligandwithanappropriateprimaryaminesleads
in a template-controlled reaction to the desired complexes with NS donor functions [55].
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