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33645545121
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note
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This acronym is based on the bisfulvalene nomenclature.
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24
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4243554051
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30
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33645548671
-
-
note
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See Figures S1-S3 in the Supporting Information for these spectra and a more detailed discussion of the NMR data.
-
-
-
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31
-
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33645544891
-
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See Figure S4, as well as Table S1, in the Supporting Information
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See Figure S4, as well as Table S1, in the Supporting Information.
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-
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33
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0007164583
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Le Vanda, C.; Bechgaard, K.; Cowan, D. O.; Müller-Westhoff, U. T.; Eilbracht, P.; Candela, G. A.; Collins, R. L. J. Am. Chem. Soc. 1976, 98, 3181.
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35
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33645549341
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note
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5h symmetry (cf. Supporting Information Figures S7 and S8).
-
-
-
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36
-
-
33645554106
-
-
note
-
The low-energy shift of the Co orbitals is more pronounced, the higher the metal character is. The HOMO of the cobaltocenium unit is therefore calculated to be of ligand type.
-
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37
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33947293342
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Sohn, Y. S.; Hendrickson, D. N.; Gray, H. B. J. Am Chem. Soc. 1971, 93, 3603.
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33645534534
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note
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-1).
-
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39
-
-
33645541052
-
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note
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The orbital mixing coefficient, α, is defined as being positive; the particular phases in 1 and 2 derive from the fact that the two metallocene units are connected via the cp rings and not via a direct metal-metal interaction.
-
-
-
-
40
-
-
33645545654
-
-
note
-
Co orbitals are admixed with ligand (cp) orbitals as in ferrocene and cobaltocenium, respectively (i.e., we are effectively considering subunit MOs).
-
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41
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33645548983
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Lever, A. B. P., Ed.; Elsevier: New York
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33645541740
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note
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The ED intensity of all of these transitions is the result of the admixture of ligand (cp) orbitals and the loss of inversion symmetry in the coupled system.
-
-
-
-
44
-
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33645553895
-
-
see Supporting Information for these values
-
These values have been derived from the ratio of the coefficients of the pure Fe and Co d orbitals (see Supporting Information for these values) in the HOMO and the LUMO, assuming that these coefficients are proportional to the coefficients of the corresponding metal-ligand admixed subunit orbitals, in the sense of ref 29.
-
-
-
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48
-
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33645536735
-
-
note
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-1 for ΔG° has been taken.
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49
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0001544463
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s were taken from the following: (a) Chang, J. P.; Fung, E. Y.; Curtis, J. C. Inorg. Chem. 1986, 25, 4233.
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51
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33645548774
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note
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Since in dichloromethane solution the observed transition energies in metallocenic systems often show a stronger red shift than the expected one, this value has not been taken into account for the linear regression (ref 1g and references therein).
-
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53
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33645546884
-
-
note
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Only the acetonitrile data were taken into account for the known reasons.
-
-
-
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54
-
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33645544229
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note
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In dichloromethane, the bandwidths are significantly smaller.
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55
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0001306951
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33645553279
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see ref 43
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Since the IVCT band of the bisfulvalenediiron cation has been reported to be nearly solvent independent (see ref 43), the resulting outer-sphere reorganization energy is zero.
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