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note
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We performed quantitative analysis of the exchange rate constants in complex 2 in various solvents and at various temperatures (see ref 10). It was found that the constants are representative of a complex process involving solvent dissociation. Our computational results support this conclusion. Thus, the C-H reductive elimination/oxidative addition mechanism in complexes 2 and 4 appears to be difficult to assess by SST quantitative analysis (although in complex 2 rates of various exchange processes can be compared).
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23
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0000598513
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2O in a variety of organic substrates: Klei, S. R.; Golden, J. T.; Tilley, T. D.; Bergman, R. G. J. Am. Chem. Soc. 2002, 124, 2092.
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0041288651
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note
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A high-energy process (barrier of 15.8 kcal/mol), involving concerted C-H reductive elimination and MeOH loss to form 5 directly from 7, was also found.
-
-
-
-
28
-
-
0041789200
-
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note
-
No exchange pathway involving rotation of the Ph ring was found to take place directly form the agostic complex 7.
-
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29
-
-
0042290365
-
-
note
-
The value of ΔG‡ for this barrier is probably underestimated due to hydrogen bonding in the TS between the H atom of the dissociated methanol and the O atom of the coordinated methanol.
-
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30
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0041288652
-
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note
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No analogue of 9 with two coordinated MeOH molecules was found, Repeated attempts to locate this minimum resulted in the convergence to 8.
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Natural population analysis (NPA) [ref 45].
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33
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0042290364
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note
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A slightly arenium character of 7 is demonstrated by the bond lengths and bond orders alternation in the aromatic ring, although most of the positive charge is still localized on the metal center, similarly to the system reported in ref 8a.
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34
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0042540974
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