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0042480243
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The PM3 method was also used, but the results correlate better with the MNDO calculations.
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42
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0042981179
-
-
note
-
The reactions were carried out in more concentrated solutions, [PhLi] = [1] = 0.2 M, and under these conditions the existence of 5 can be appreciated.
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44
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0042480237
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note
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We carried out the semiempirical studies with MNDO and PM3. Both methods gave us similar geometrical results but dissimilar relative energies. The previous successful use of MNDO for calculations of very closely related structures (cinnamyl and aryl derivatives, see references 16(b) and (c)) led us to take the decision to present only the MNDO results.
-
-
-
-
50
-
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84961980743
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COSMO (conductor-like screening model) evaluates the solvent screening energy for a cavity based on the solvent-accessible surfaces and for a charge distribution derived from a distributed multipole analysis: A. Klamt and G. Schüürmann, J. Chem. Soc., Perkin Trans. 2, 1993, 799.
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51
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0041478429
-
-
note
-
The calculated alternative pathways were: (a) attack of monomeric PhLi and similar rearrangement with a [1,2]-hydride shift; (b) previous deaggregation of dimer PhLi and attack followed by the [1,2]-hydride rearrangement; (c) addition of PhLi followed by attack of a second lithium with [1,2]-hydride shift and (d) attack of dimer PhLi with H shift from the carbonyl C to O. Options (a) and (b) seem attractive but the energetic changes in these options were unfavorable.
-
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-
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52
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0001605768
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E. Kauffmann, J. Gose and P. v. R. Schleyer, Organometallics, 1989, 8, 2577.
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53
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33947294592
-
-
3 arrangement, with the lithium atom coordinately bonded to the benzylic C, C ipso and C ortho, is also observed in the X-ray structure of benzyllithium, in S. P. Patterman, I. L. Karle and G. D. Stucky, J. Am. Chem. Soc., 1970, 92, 1150.
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54
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0041478428
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note
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We thank one of the referees for this comment.
-
-
-
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55
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0003467672
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Wiley-Interscience, New York, ch. 18
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March, J.1
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56
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0030861104
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For a number of previous calculations in which discrete solvation was used see: (a) J. F. Remenar, B. L. Lucht and D. B. Collum, J. Am. Chem. Soc., 1997, 119, 5567;
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Remenar, J.F.1
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0030698167
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(b) A. Abbotto, A. Streitwieser and P. v. R. Schleyer, J. Am. Chem. Soc., 1997, 119, 11255;
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Abbotto, A.1
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0000315067
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(d)refs. 17(b), 21(d)
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(c) F. E. Romesberg and D. B. Collum, J. Am. Chem. Soc., 1992, 114, 2112; (d)refs. 17(b), 21(d).
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Romesberg, F.E.1
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Other "dielectric continuum" models are: (a) G. P. Ford and B. Wang, J. Am. Chem. Soc., 1992, 114, 10563;
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(c) H. S. Rzepa, M. M. Yi, M. M. Karelson and M. C. Zerner, J. Chem. Soc., Perkin Trans. 2, 1991, 635;
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Rzepa, H.S.1
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64
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0042981176
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note
-
The reaction of 2 equivalents of PhLi with 2, at 20 °C in THF gives only 79% of 5 and 21% of 4.
-
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65
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0001493946
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