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Norman, N.C.7
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(b) Clegg, W.; Dai, C.; Lawlor, F. J.; Marder, T. B.; Nguyen, P.; Norman, N. C.; Pickett, N. L. Power, W. P.; Scott, A. J. Chem. Soc., Dalton Trans. 1997, 839.
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Clegg, W.1
Dai, C.2
Lawlor, F.J.3
Marder, T.B.4
Nguyen, P.5
Norman, N.C.6
Pickett, N.L.7
Power, W.P.8
Scott, A.9
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(c) Clegg, W.; Scott, A. J.; Souza, F. E. S.; Marder, T. B. Acta Crystallogr. 1999, C55, 1885.
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Clegg, W.1
Scott, A.J.2
Souza, F.E.S.3
Marder, T.B.4
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note
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(a) Since the dissociative substitution followed by the trans-metalation is less favorable than the associative substitution followed by the transmetalation, as described in the text, the reaction course involving the dissociative substitution is not investigated in detail here. Thus, we roughly estimated the activation barrier by calculating the energy change as a function of the X-Pd-P angle (X = HO, F, or Cl).
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(b) Because of the above reason, we did not optimize the transition state of this process.
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116
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84962451250
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note
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3 complexes to real phosphine complexes.
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117
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84962417381
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note
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(b) The solvent molecule stabilizes the coordinatively unsaturated intermediate through the coordination. However, the dissociation of phosphine must occur first in the dissociative substitution. Thus, it is likely to consider that the rate-determining step is dissociation of phosphine.
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118
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0034683363
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Biswas, B.; Sugimoto, M.; Sakaki, S. Organometallics 2000, 19, 3895.
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(2000)
Organometallics
, vol.19
, pp. 3895
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Biswas, B.1
Sugimoto, M.2
Sakaki, S.3
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Amatore, C.; Jutand, A.; Thuilliez, A. Organometallics 2001, 20, 3241.
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Organometallics
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, pp. 3241
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Amatore, C.1
Jutand, A.2
Thuilliez, A.3
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Biswas, B.; Sugimoto, M.; Sakaki, S. Organometallics 1999, 18, 4015.
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(1999)
Organometallics
, vol.18
, pp. 4015
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Biswas, B.1
Sugimoto, M.2
Sakaki, S.3
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π bonding interaction between the X and Beg groups; the B-O distance is 1.378Å in HO-Beg. 1.368Å in F-Beg, 1.364Å in Cl-Beg, and 1.360Å in I-Beg. These results clearly indicate that the π-bonding interaction between I and Beg groups is very weak.
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AcO-Beg bond energy is calculated to be 130.0 kcal/mol with the DFT/BS-II/DFT/BS-I method. This value is smaller than the HO-Beg and F-Beg bond energies but much larger than the Cl-Beg bond energy. Although the Pd-OAc and Pd-(AcO-Beg) bond energies should be considered in the discussion, the large AcO-Beg bond energy suggests that the palladium acetate complex is one of candidates of good catalysts. Actually, the AcO salt was experimentally used in the first report of Ishiyama et al.
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