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The bond angles calculated at the level of CPCM-MP2/6-31+G(d) and CPCM-MP2/6-311+G(3df,2p) are summarized in Supporting Information
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The bond angles calculated at the level of CPCM-MP2/6-31+G(d) and CPCM-MP2/6-311+G(3df,2p) are summarized in Supporting Information.
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79953243260
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The secondary normal β-type-DKIEs,kH/kD >1, involving the rate-limiting leaving group expulsion from the intermediate can be obtained: kH/kD = 1.03-1.11 for the reactions of phenylacetyl chlorides with deuterated anilines in MeCN Harper and Row: New York, 1987; (ii) kH/kD = 1.04-1.12 for the reactions of 4-nitrophenyl N-phenylcarbamates with deuterated benzylamines in MeCN (Koh, H. J.; Kim, O. S.; Lee, H. W.; Lee, I. J. Phys. Org. Chem. 1997, 10, 725); (iii) kH/kD = 1.02-1.11 for the reactions of benzhydryl chlorides with deuterated pyrrolidine in MeCN (Chang, S.; Koh, H. J.; Lee, B. S.; Lee, I. J. Org. Chem. 1995, 60, 7760); and (iv) The obtained order of 1.1 is consistent with the typical value of the secondary normal β-DKIEs. (Lowry, T. H.; Richardson, K. S. Mechanism and Theory in Organic Chemistry, 3rd ed.
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The secondary normal β-type-DKIEs, kH/kD > 1, involving the rate-limiting leaving group expulsion from the intermediate can be obtained: kH/kD = 1.03-1.11 for the reactions of phenylacetyl chlorides with deuterated anilines in MeCN (Lee, H. W.; Lee, J. W.; Koh, H. J.; Lee, I. Bull. Korean Chem. Soc. 1998, 19, 642); (ii) kH/kD = 1.04-1.12 for the reactions of 4-nitrophenyl N-phenylcarbamates with deuterated benzylamines in MeCN (Koh, H. J.; Kim, O. S.; Lee, H. W.; Lee, I. J. Phys. Org. Chem. 1997, 10, 725); (iii) kH/kD = 1.02-1.11 for the reactions of benzhydryl chlorides with deuterated pyrrolidine in MeCN (Chang, S.; Koh, H. J.; Lee, B. S.; Lee, I. J. Org. Chem. 1995, 60, 7760); and (iv) The obtained order of 1.1 is consistent with the typical value of the secondary normal β-DKIEs. (Lowry, T. H.; Richardson, K. S. Mechanism and Theory in Organic Chemistry, 3rd ed.; Harper and Row: New York, 1987; p 239).
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79953247353
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The grouping depending on the magnitude of DKIE seems to be somewhat arbitrary. A lot of DKIEs data for the aminolyses (anilinolysis and benzylaminolyses) of various substrates involving deuterated nucleophiles have been cumulated by the authors, enough to be confident of the grouping
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The grouping depending on the magnitude of DKIE seems to be somewhat arbitrary. A lot of DKIEs data for the aminolyses (anilinolysis and benzylaminolyses) of various substrates involving deuterated nucleophiles have been cumulated by the authors, enough to be confident of the grouping.
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