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Chapter 5 Published Results Both polyanions 29 and 30a are composed of the same Keggin fragments, but there is still a major difference between them. Polyanion 29 has a plane of symmetry which passes through the rotated triad of the (B-β-GeW 9 O 34 ) unit (Figure 5.18a), while 30a lacks a plane of symmetry due to the positioning of the rotated triad “on the side” of the polyanion (Figure 5.18b). Figure 5.18. Polyhedral representation of the copper(II) containing 29 (left, a) and the cobalt(II) containing fragment 30a (right, b). Notice the different orientation of the rotated triad in the respective “upper” (B-β-GeW 9 O 34 ) units. We believe that the different electron configurations and hence coordination geometries of Cu 2+ (d 9 ) and Co 2+ (high-spin d 7 ) are most likely the origin of the structural differences for 29 and 30a. Copper(II) ions exhibit the well-known Jahn-Teller distortion, resulting in axially elongated octahedral coordination. It appears that such a distorted trinuclear copper(II) cluster (Figure 5.19) can be accommodated better in the cisoid conformation of 29, whereas the trinuclear cobalt(II) cluster can be accommodated better in the transoid conformation of 30a. Taking a closer look at the Cu-O bond lengths in 29 indicates that the equatorial bonds are in the normal range (Cu1-O eq 1.95(3) Å, Cu2-O eq 1.96(2) Å, Cu3-O eq 1.98(1) Å). As expected, 207
Chapter 5 Published Results the axial Cu-O bonds are longer and actually fall in the two categories long and very long (Cu1-O ax 2.35(1), 2.55(1) Å; Cu2-O ax 2.30(1), 2.54(1) Å; Cu3-O ax 2.31(1), 2.52(1) Å), (Table 5.7). Figure 5.19. Ball-and-stick representation of the Cu 3 -core of 29 and the labeling scheme. We also performed BVS calculations for 30. The values for two of the oxygens, O2C7 (0.23) and O3C7 (0.29), connected to the Co linker in 30 show that they are diprotonated. In addition, we discovered monoprotonation in each of the (B-β-GeW 9 O 34 ) units, one of them being O26A (1.10) in the first sandwich-type fragment and the second being O3C3 (1.09) in the other fragment. Moreover, a proton is disordered over two positions in each (B-β- GeW 8 O 31 ) unit. The first proton is shared by oxygens O137 (1.27) and O146 (1.40) in the first fragment and the other by O272 (1.53) and O283 (1.43). 208
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