Preorganization of tetrathiamacrocyclic ligands: implications from computed and experimentally determined structures
1997
The tetrathiamacrocycles
trans-6,13-dihydroxy-1,4,8,11-tetrathiacyclotetradecane
(L
1
) and its benzo- (L
2
), syn- and
anti-dibenzo-substituted derivatives (L
3
and
L
3′
, respectively) have been prepared by conventional
methods, and a benzo-substituted-1,4,7,10-tetrathiacyclotridecane
(L
4
) was obtained by substitution of
o-dichlorobenzene after activation with an organometallic
fragment. The structures of L
1
–L
4
and of the
four palladium(II) complexes
[PdL
1
]Cl
2
·2H
2
O,
[PdL
2
][PF
6
]
2
,
[PdL
3′
][PF
6
]Cl and
[PdL
4
][PF
6
]
2
were determined by X-ray
crystallography. All the experimentally determined structures were
accurately reproduced by molecular mechanics calculations, using a
constant-parametrization scheme. Two parameters for the evaluation of
the extent of preorganization of free macrocycle molecules, based on
structural and strain-energy differences of the free macrocycles and
their corresponding metal complexes, are introduced and discussed on the
basis of the experimentally determined and computed structural data for
L
1
–L
4
, their metal complexes and other
similar ligand and metal complex systems. The implications for the
design of new compounds leading to high stability and high metal-ion
selectivity are outlined.
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