Table 7 Summary of residual strain energies for copper() and copper() complexes with [14]aneS4-a, [14]aneS4-b, [14]aneNS3-a and [14]aneNS3-b
Conf I
Conf IIAa
Conf IIBb
Conf IICc
Conf III
Conf V
Copper()
Copper()
[14]aneS4-a
[14]aneS4-b
[14]aneNS3-a
[14]aneNS3-b
3.08
4.78
4.90
7.01
9.11
14.18a
6.40d
9.97a
–
–
4.53
9.56
5.35
7.56
24.93
27.10
NOg
NOg
10.12b
8.84e
8.03b
10.81c
9.88f
13.04c
[14]aneS4-a
[14]aneS4-b
[14]aneNS3-a
[14]aneNS3-b
43.29
39.49
41.19
44.26
32.10
24.44a
27.49d
25.7a
–
–
62.65
NOg
56.94
NOg
16.72
16.02
14.51
15.98
28.70b
28.93e
31.08b
33.48c
21.01f
24.01c
a For the [14]aneS4-b and [14]aneNS3-b complexes, the unique donor atom in Conf IIA is the one adjacent to the 5,5 linkages (i.e., N in the case
of [14]aneNS3-b). b For the [14]aneS4-b and [14]aneNS3-b complexes, the unique donor atom in Conf IIB is the sulfur adjacent to the 5,6 linkages.
c For the [14]aneS4-b and [14]aneNS3-b complexes, the unique donor atom in Conf IIC is the sulfur adjacent to the 6,6 linkages. d For the [14]ane-
NS3-a complexes, the unique donor atom in Conf IIA is nitrogen. e For the [14]aneNS3-a complexes, the unique donor atom in Conf IIB is the sulfur
closest to the nitrogen. f For the [14]aneNS3-a complexes, the unique donor atom in Conf IIC is the sulfur furthest from the nitrogen. g The strain
energies for these conformers could not be minimized.
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species.) In fact, for the two NS3 ligands, the oxidized complexes
could not be minimized in conformer V without “freezing” the
positions of three or more atoms. The data also support
the premise that conformer V is the most stable geometry
for the CuIL species and conformer II appears to be much
more stable than either conformer I or III for these reduced
species.
All of the kinetic data obtained in this study, in conjunction
with the qualitative molecular mechanical calculations are con-
sistent with our earlier postulate13 that the II
V inter-
conversion represents the discrete conformational step during
the overall electron-transfer reaction, that is, the latter con-
formational change is presumed to represent the dominant
energy barrier for both vertical steps in Fig. 1. This implies that,
in the case of the Cu(/) systems involving the a isomers,
species O represents the (rapidly) equilibrated mixture of con-
formers III (or I) and II, and intermediates P and Q represent
conformers II and V, respectively. The apparently anomalous
behavior of the system involving [14]aneS4-a may be attribut-
able to a smaller barrier in the II
V conformational change,
but this hypothesis cannot be confirmed on the basis of data
currently available.
Acknowledgements
This work was supported by the US National Science Found-
ation under Grants CHE-9528831 and CHE-9817919.
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D a l t o n T r a n s . , 2 0 0 3 , 1 5 7 7 – 1 5 8 6
1585