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Use of Wilke's Azaphospholene (L1): (a) Wegner, A.; Leitner, W. Chem. Commun. 1999, 1583, and references therein.
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Use of Wilke's Azaphospholene (L1): (a) Wegner, A.; Leitner, W. Chem. Commun. 1999, 1583, and references therein.
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8
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0033610498
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Phospholanes as ligands: (b) Nandi, M.; Jin, J.; RajanBabu, T. V. J. Am. Chem. Soc. 1999, 121, 9899.
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Phospholanes as ligands: (b) Nandi, M.; Jin, J.; RajanBabu, T. V. J. Am. Chem. Soc. 1999, 121, 9899.
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10
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0037028566
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Phosphiniates: (d) Park, H.; RajanBabu, T. V. J. Am. Chem. Soc. 2002, 124, 734.
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Phosphiniates: (d) Park, H.; RajanBabu, T. V. J. Am. Chem. Soc. 2002, 124, 734.
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11
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0037028545
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Phosphoramidites: (e) Franció, G.; Faraone, F.; Leitner, W. J. Am. Chem. Soc. 2002, 124, 736.
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Phosphoramidites: (e) Franció, G.; Faraone, F.; Leitner, W. J. Am. Chem. Soc. 2002, 124, 736.
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12
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20444481391
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(f) Park, H.; Kumareswaran, R.; RajanBabu, T. V. Tetrahedron 2005, 61, 6352.
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Park, H.1
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Details of preparative methods: Smith, C. R.; Zhang, A.; Mans, D. J.; RajanBabu, T. V. Org. Synth. 2008, 85, 248.
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(j) Details of preparative methods: Smith, C. R.; Zhang, A.; Mans, D. J.; RajanBabu, T. V. Org. Synth. 2008, 85, 248.
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47349105054
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3-allyl-Palladium(II) Complexes, Ph.D. Thesis University of North Carolina, 1997. We thank Professor Brookhart and Dr. DiRenzo for a copy of this dissertation.
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67449129307
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Frisch, M. J.; et al. Gaussian 03; Gaussian, Inc.: Pittsburgh, PA, 2003 (See Supporting Information for a complete list of authors).
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Frisch, M. J.; et al. Gaussian 03; Gaussian, Inc.: Pittsburgh, PA, 2003 (See Supporting Information for a complete list of authors).
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33
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67449165698
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We have also checked the effect of diffuse functions, as per the suggestion of one of the referees, on the energetics of two important steps at B3LYP/6-31, G*//B3LYP/6-31G* (and also at B3LYP/6-31, G*; given in parentheses below, The energy difference for 40 viz, 40S, 40R [vide infra, see text] changes from, 0.6 kcal/mol to, 0.5, 0.6) kcal/mol in the same direction. So is the case for 99, viz, 99RS, 99RR, which is now, 0.4 (0.3) kcal/mol versus the previous, 0.6 kcal/mol. The new activation energy for initiation is 19.2 (18.6) kcal/mol for S versus the earlier 18.8 kcal/mol, and for R 19.8 (19.2) kcal/mol versus the earlier 19.5 kcal/mol. The activation energy, 99RS, 86R, of the catalytic cycle is now
-
*; given in parentheses below). The energy difference for 40 viz., 40S - 40R [vide infra, see text] changes from - 0.6 kcal/mol to - 0.5 (-0.6) kcal/mol in the same direction. So is the case for 99, viz., 99RS - 99RR, which is now - 0.4 (0.3) kcal/mol versus the previous - 0.6 kcal/mol. The new activation energy for initiation is 19.2 (18.6) kcal/mol for S versus the earlier 18.8 kcal/mol, and for R 19.8 (19.2) kcal/mol versus the earlier 19.5 kcal/mol. The activation energy, 99RS - 86R, of the catalytic cycle is now
-
-
-
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34
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9144243036
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(a) Hölscher, M.; Franciò, G.; Leitner, W. Organometallics 2004, 23, 5606.
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Hölscher, M.1
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35
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21844505539
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For a limited molecular model study, see: b
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Angermund, K.1
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36
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67449169199
-
-
This conformational search was carried out using the known bonding pattern of the system, which has only the usual chemical bonds; thus the search involved rotation across the bonds. A number of conformers of very close energy to the lowest conformer exist for many of the points in Figure 2. These were ignored from consideration for the discussion, although they are also populated
-
This conformational search was carried out using the known bonding pattern of the system, which has only the usual chemical bonds; thus the search involved rotation across the bonds. A number of conformers of very close energy to the lowest conformer exist for many of the points in Figure 2. These were ignored from consideration for the discussion, although they are also populated.
-
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37
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22944469409
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For a recent DFT study
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(a) For a recent DFT study: Ariafard, A.; Lin, Z. Organometallics 2005, 24, 3800.
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33847089848
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For previous theoretical studies of bonding in allyl systems, see: b
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0003625966
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Wilkinson, G, Ed, Pergamon: Oxford, England, Chapter 19, pp
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(a) Rufinska, A.; Goddard, R.; Weidenthaler, C.; Buhl, M.; Porschke, K.-R. Organometallics 2006, 25, 2308.
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Allyl rotation mechanism in Ni(II) complexes: (b) Hampton, P. D.; Wu, S.; Alam, T. M.; Claverie, J. P. Organometallics 1994, 13, 2066.
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Allyl rotation mechanism in Ni(II) complexes: (b) Hampton, P. D.; Wu, S.; Alam, T. M.; Claverie, J. P. Organometallics 1994, 13, 2066.
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44
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0001308759
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(d) Aresta, M.; Dibenedetto, A.; Quaranta, E.; Lanfranchi, M.; Tiripicchio, A. Organometallics 2000, 19, 4199.
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46
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67449156789
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18 is slightly lower than 17 in energy without ZPE correction.
-
18 is slightly lower than 17 in energy without ZPE correction.
-
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-
-
47
-
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67449129230
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Pentacoordinate Ni-intermediates have been implicated in C, C coupling reactions and reductive eliminations, see: (a) Shultz, C. S, DeSimone, J. M, Brookhart, M. J. Am. Chem. Soc. 2001, 123, 9172
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Pentacoordinate Ni-intermediates have been implicated in C - C coupling reactions and reductive eliminations, see: (a) Shultz, C. S.; DeSimone, J. M.; Brookhart, M. J. Am. Chem. Soc. 2001, 123, 9172.
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48
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8181. Chemistry of five-coordinate Ni(II)allyl complexes
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84868991798
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It may be noted that the transition state 34 is very much lower in energy than isoelectronic analogues, for example, tetrahedral 10 (Scheme 6, whereη3-allyl was not flexible enough to make room for the ligand substituents as in 34, which may be considered as a trigonal pyramid (rather than tetrahedral, with olefin in the plane of P and O Scheme 12
-
3-allyl was not flexible enough to make room for the ligand substituents as in 34, which may be considered as a trigonal pyramid (rather than tetrahedral), with olefin in the plane of P and O (Scheme 12).
-
-
-
-
50
-
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0031020614
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For a similar result in the computational studies of Ni(II)-catalyzed polymerization/oligomerization of ethylene, see: (a) Deng, L.; Margl, P.; Ziegler, T. J. Am. Chem. Soc. 1997, 119, 1094.
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For a similar result in the computational studies of Ni(II)-catalyzed polymerization/oligomerization of ethylene, see: (a) Deng, L.; Margl, P.; Ziegler, T. J. Am. Chem. Soc. 1997, 119, 1094.
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