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3743056652
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note
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+ we find a reaction energy and zero-point reaction enthalpy of-80 and -57 kJ/mol, respectively, whereas the corresponding numbers for the insertion barrier are 26 and 33 kJ/mol. This agrees well with our expectations and leaves considerable justification for using the calculated activation energies in a discussion of the experiments.
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41
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0024092618
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46
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3743153585
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note
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In Figure 7A, we have omitted the data from runs 6 and 22 from the FTIR measurements and run 15 from the GPC measurement because these values clearly deviate more than 3 times the standard deviation of the data.
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49
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0000729950
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Eisch, J.; Caldwell, K.; Werner, S.; Kruger, C. Organometallics 1991, 10, 3417-3419.
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0031380472
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Some attempts to model the influence of MAO on the polymerization have appeared in the literature lately, see, e.g., ref 10 and: Fusco, R.; Longo, L.; Masi, F.; Garbassi, F. Macromolecules 1997, 30, 7673-7685.
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Fusco, R.1
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52
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85088075949
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note
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-1.
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53
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3743061167
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note
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Some of the calculations with L = Cp were performed with a propyl chain, whereas with L = Cp*, we have always started with a butyl chain. With β-agostic structures, we have verified that there are only minor differences between results based on a propyl and a butyl chain. However, in connection with the isomerization reaction, it is necessary to use at least a butyl chain.
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54
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85088078437
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note
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β.
-
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55
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3743060058
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note
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Backside insertion into a γ-agostic structure has been attempted but found to be extremely unlikely. The activation energy is more than 170 kJ/mol, even with L = Cp.
-
-
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56
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3743061166
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note
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An attempt to model termination by transfer of a γ-hydrogen shows that it is highly unlikely. This is as expected, since it would have to be accompanied by additional hydrogen migration.
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