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53549124210
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For computational details, see the Supporting Information
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For computational details, see the Supporting Information.
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25
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35548929060
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53549132615
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For details, see the Supporting Information
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For details, see the Supporting Information.
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53549092333
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Our calculations carried out for the, tBu)3P] ⋯[B(C6H5)3] adduct underline the importance of C-H⋯F interactions to the bonding in, tBu) 3P]⋯[B(C6F5)3, but our results also indicate that their presence is not a prerequisite in the formation of frustrated complexes for details, see the Supporting Information
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3], but our results also indicate that their presence is not a prerequisite in the formation of frustrated complexes (for details, see the Supporting Information).
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29
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53549133745
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The exothermicity of association is likely overcompensated by entropy loss, may not be obvious
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3] adducts may not be obvious.
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3] adducts
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30
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53549100559
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Geometry optimization following initial IRC calculation leads to a very shallow energy minimum corresponding to a structure wherein H2 is weakly bound to an open form of the, tBu)3P]⋯[B(C 6F5)3] adduct; in the other direction, the, tBu)3PH][HB(C6F5)3] product is obtained see the Supporting Information
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3] product is obtained (see the Supporting Information).
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31
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0037167050
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The TS we located bears common structural features with that identified by Chan and Radom for base-catalyzed hydrogenation of ketones. For detailed kinetic and computational studies, see: a A. Berkessel, T. J. S. Schubert, T. N. Müller, J. Am. Chem. Soc. 2002, 124, 8693;
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The TS we located bears common structural features with that identified by Chan and Radom for base-catalyzed hydrogenation of ketones. For detailed kinetic and computational studies, see: a) A. Berkessel, T. J. S. Schubert, T. N. Müller, J. Am. Chem. Soc. 2002, 124, 8693;
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33
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53549098012
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Δρ is defined as Δρ, ρ(TS)-ρ([(tBu) 3P]⋯[B(C6F5)3]*, ρ(H2*, where the atomic positions of, tBu) 3P]⋯[B(C6F5)3]* and H2* are identical to those in the TS
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2* are identical to those in the TS.
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34
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3042729899
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The importance of the preorganization of active sites for an analogous near-linear four-centered TS has already been demonstrated in Rh-assisted homolytic H2 activation, albeit involving the intramolecular use of two metalloradical centers. See: W. Cui, B. B. Wayland, J. Am. Chem. Soc. 2004, 126, 8266
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2 activation, albeit involving the intramolecular use of two metalloradical centers. See: W. Cui, B. B. Wayland, J. Am. Chem. Soc. 2004, 126, 8266.
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34250366259
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The frustration energy can be quantified, for instance, by carrying out activation-strain analysis as proposed by Bickelhaupt and co-workers. See
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The frustration energy can be quantified, for instance, by carrying out activation-strain analysis as proposed by Bickelhaupt and co-workers. See: G. T. de Jong, F. M. Bickelhaupt, ChemPhysChem 2007, 8, 1170.
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(2007)
ChemPhysChem
, vol.8
, pp. 1170
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de Jong, G.T.1
Bickelhaupt, F.M.2
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36
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53549130792
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Frustrated complexes, C6H2Me3) 3P]⋯[B(C6F5)3] and, C 6F5)2B-C6F4-P(tBu) 2]⋯[(C6F5)2B-C 6F4-P(tBu)2] have also been identified in our calculations see the Supporting Information
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2] have also been identified in our calculations (see the Supporting Information).
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