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1-bridging ethyl groups. However, the shortening of these C-C bonds might also be caused by higher librational motion and/or some degree of disorder due to the higher structural flexibility of these noncoordinated ethyl groups. Unfortunately, we could not sort out this problem by a high-resolution low-temperature X-ray study, since all investigated crystals of 3 start to powderize at temperatures below -50 °C; see: Scherer, W.; Heiringer, W.; Spiegler, M.; Sirsch, P.; McGrady, G. S.; Downs, A. J.; Haaland, A.; Pedersen, B. Chem. Commun. 1998, 2471-2472.
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13C NMR spectra are rather small.
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1. We have therefore used the expression "polarization of the outer shell of the core of the Y atom" to account for the occurrence of CPs in the fourth shell of the Y atom. However, valence shell electrons and outer core electrons, as defined by the orbital model, cannot be distinguished on the basis of the Laplacian for elements beyond argon (see, e.g.: Sagar, R. P.; Ku, A. C. T.; Smith, V. H., Jr.; Simas, A. M. J. Chem. Phys. 1988, 88, 4367-4374).
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Indeed, studies comparing the results of calculations using all-electron bais sets or effective core potentials have clearly demonstrated that the occurrence of CPs in the outer shell of elements beyond argon has to be attributed mainly to a polarization of the valence electrons and outer core electrons MacDougall, P. J.; Hall, M. B. Trans. Am. Crystallogr. Assoc. 1990, 26, 105-123.
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We note that in the case of 5 even six local charge concentrations are observed. It remains to be clarified whether the different numbers of these domains (six in 5 and five in 6) and their mutual arrangements are a consequence of the different bridging groups (methyl vs ethyl) attached to the Y center. Indeed, the calculated Y-C bond distances in 5 are ∼0.02 Å shorter than those in 6, suggesting a stronger Y-C bonding in 5. Thus, the ligand-induced charge polarization in 5 might be more pronounced compared with 6, causing the formation of six CCs in 5 vs. five CCs in 6.
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We note that in the case of 5 six CCs form a slightly distorted trigonal antiprism.
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