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2642663951
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note
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2 by 1.0 kcal/mol at (8,8)CASSCF/6-31G* and by 2.0 kcal/mol at (8,8)CASPT2N/6-31G*.
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24
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2642598490
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note
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3-PyCH was chosen over 2-PyCH for detailed study because the interaction between the ring nitrogen and the divalent carbon atom is smaller in the former carbene than in the latter. For example, whereas, at the CASPT2N level, the syn and anti geometries differ in energy by only 0.3 kcal/mol in singlet 3-PyCH, they differ by 3.6 kcal/mol in singlet 2-PyCH. The greater similarity in energies of the syn and anti conformers of 3-PyCH, compared to 2-PyCH, thus makes 3-PyCH a better model for PhCH, for which the analogous conformers are degenerate.
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25
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2642693152
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note
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3A″ states of PhCH).
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27
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36448998619
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Andersson, K.1
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28
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0041401966
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The G2 method gives energies that are effectively equivalent to QCISD(T)/6-311+G(3df, 2p)//Full-MP2/6-31G* calculations, which are then corrected with scaled HF/6-31G* zero-point and thermal corrections to obtain enthalpies at 298 K. [Curtiss, L. A.; Raghavachari, K.; Trucks, G. W.; Pople, J. A. J. Chem. Phys. 1991, 94, 7221.]
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MOLCAS version 3; Andersson, K.; Blomberg, M. R. A.; Fülscher, M. P.; Kellö, V.; Lindh, R.; Malmqvist, P.-Å.; Noga, J.; Olsen, J.; Roos, B. O.; Sadlej, A. J.; Siegbahn, P. E. M.; Urban, M.; Widmark, P.-O.; University of Lund, Sweden, 1994.
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Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Keith, T.; Petersson, G. A.; Montgomery, J. A.; Raghavachari, K.; Al-Laham, M. A.; Zakrzewski, V. G.; Ortiz, J. V.; Foresman, J. B.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; Wong, M. W.; Andres, J. L.; Replogle, E. S.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Binkley, J. S.; Defrees, D. J.; Baker, J.; Stewart, J. P.; Head-Gordon, M.; Gonzalez, C.; Pople, J. A.; Gaussian 94, Revision B.3; Gaussian, Inc.: Pittsburgh, PA, 1995.
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Johnson, B.G.5
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Cheeseman, J.R.7
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Montgomery, J.A.10
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Zakrzewski, V.G.13
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Foresman, J.B.15
Peng, C.Y.16
Ayala, P.Y.17
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Defrees, D.J.26
Baker, J.27
Stewart, J.P.28
Head-Gordon, M.29
Gonzalez, C.30
Pople, J.A.31
more..
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37
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2642594515
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note
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Since the energy of syn-3-PyCH is lower than that of the anti-3-PyCH in both the lowest singlet and triplet states, the energies computed for the syn stereoisomer are those that are reported in Table 1.
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38
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2642596538
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note
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2.
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39
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2642685024
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note
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12
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40
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2642691145
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note
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2 should indeed be stronger than an N-H bond formed by triplet NH.
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41
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0003363438
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Neutral Thermochemical Data
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Mallard, W. G., Linstrom, P. J., Eds.; National Institute of Standards and Technology: Gaithersburg, MD 20899, August 1997
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(a) Afeefy, H. Y.; Liebman, J. F.; Stein, S. E. Neutral Thermochemical Data. In NIST Standard Reference Database Number 69; Mallard, W. G., Linstrom, P. J., Eds.; National Institute of Standards and Technology: Gaithersburg, MD 20899, August 1997 (http://webbook.nist.gov).
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NIST Standard Reference Database Number 69
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Afeefy, H.Y.1
Liebman, J.F.2
Stein, S.E.3
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4. [Sun, H.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1987, 109, 5275].
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Sun, H.1
Hrovat, D.A.2
Borden, W.T.3
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