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56349094298
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chem.200800715, preceding paper in this issue, DOI: 10.1002
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T. Strenalyuk, A. Haaland. Chem. Eur. J. 2008, 14, DOI: 10.1002/ chem.200800715, preceding paper in this issue.
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(2008)
Chem. Eur. J
, vol.14
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Strenalyuk, T.1
Haaland, A.2
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3
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4744349320
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The topic was for the first time discussed in an earlier paper by
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The topic was for the first time discussed in an earlier paper by A. Haaland. D. J. Shorokhov, N. V. Tverdova, Chem. Eur. J. 2004, 10, 4416.
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(2004)
Chem. Eur. J
, vol.10
, pp. 4416
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Haaland, A.1
Shorokhov, D.J.2
Tverdova, N.V.3
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4
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33645325939
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The arguments in this paper were supported by J. Poater, M. Solà, F. M. Bickelhaupt, Chem. Eur. J. 2006, 12, 2902
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The arguments in this paper were supported by J. Poater, M. Solà, F. M. Bickelhaupt, Chem. Eur. J. 2006, 12, 2902.
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5
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35348949003
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Opposing views have been published in reference [2] and by A. Krapp, G. Frenking, Chem. Eur. J. 2007, 13, 8256.
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Opposing views have been published in reference [2] and by A. Krapp, G. Frenking, Chem. Eur. J. 2007, 13, 8256.
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7
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56349084951
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The MP2/6, 311G(2d.2p) calculations were performed using Gaussian 03, Revision C.02. M. J. Frisch, G. W. Trucks, H. B. Schlegel. G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr, T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Pelersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Danneriberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Marti
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The MP2/6 + + 311G(2d.2p) calculations were performed using Gaussian 03, Revision C.02. M. J. Frisch, G. W. Trucks, H. B. Schlegel. G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr., T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Pelersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Danneriberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, J. A. Pople, Gaussian, Inc., Wallingford CT, 2004. AIM analyses of the electron densities were performed using AIMAll (Version 08.05.04), Todd A. Keith, 2008 (aim.tkgristmill.com). The contour line diagrams were generated using AIMPAC: R. F. W. Bader: http://www.chemistry.mcmaster.ca/ aimpac/imagemap/imagemap.htm.
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8
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0042434872
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W. Koch, G Frenking, J. Gauss, D. Cremer, J. B. Collins, J. Am. Chem. Soc. 1987, 109, 5917.
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(1987)
J. Am. Chem. Soc
, vol.109
, pp. 5917
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Koch, W.1
Frenking, G.2
Gauss, J.3
Cremer, D.4
Collins, J.B.5
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11
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15044357417
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a) A. Kovács, C Esterhuysen, G. Frenking, Chem. Eur. J. 2005, 11, 1813;
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(2005)
Chem. Eur. J
, vol.11
, pp. 1813
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Kovács, A.1
Esterhuysen, C.2
Frenking, G.3
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12
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33845734259
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b) A. Krapp, F. M. Bickelhaupt, G. Frenking, Chem. Eur. J. 2006, 12, 9196.
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(2006)
Chem. Eur. J
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, pp. 9196
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Krapp, A.1
Bickelhaupt, F.M.2
Frenking, G.3
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13
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56349155480
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A mathematical explanation for this finding is given in: a W. Kutzelnigg in: The Concept of the Chemical Bond, 1 (Ed.: Z. B. Maksic), Springer, Berlin/Heidelberg, 1990, p. 1;
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A mathematical explanation for this finding is given in: a) W. Kutzelnigg in: The Concept of the Chemical Bond, Vol. 1 (Ed.: Z. B. Maksic), Springer, Berlin/Heidelberg, 1990, p. 1;
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16
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56349095041
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For a more detailed discussion see reference [7b
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For a more detailed discussion see reference [7b].
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17
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56349166922
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The same statement holds true for steric repulsion between bulky substituents which are often wrongly explained in terms of Coulombic repulsion between the electrons
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The same statement holds true for steric repulsion between bulky substituents which are often wrongly explained in terms of Coulombic repulsion between the electrons.
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19
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85150404301
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Recent research which is presently a hot topic in physical chemistry has shown that for a truly comprehensive understanding of chiral molecules the electroweak interactions must be considered which comprise the weak force as well as the electrostatic force: M. Quack, J. Stohner, M. Willeke, Ann. Rev. Phys. Chem. 2008, 59, 741
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Recent research which is presently a hot topic in physical chemistry has shown that for a truly comprehensive understanding of chiral molecules the electroweak interactions must be considered which comprise the weak force as well as the electrostatic force: M. Quack, J. Stohner, M. Willeke, Ann. Rev. Phys. Chem. 2008, 59, 741.
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20
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56349128099
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It is important to realize that many fundamental concepts such as the Lewis electron-pair model for covalent bonding have been introduced before modern quantum theory was developed and applied to chemistry. For a discussion of the history and the application of the Lewis electron-pair model see the special issue devoted to the topic 90 Years of Chemical Bonding: J. Comput. Chem. 2007, 28, issue 1
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It is important to realize that many fundamental concepts such as the Lewis electron-pair model for covalent bonding have been introduced before modern quantum theory was developed and applied to chemistry. For a discussion of the history and the application of the Lewis electron-pair model see the special issue devoted to the topic 90 Years of Chemical Bonding: J. Comput. Chem. 2007, 28, issue 1.
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21
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0035961576
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We give two striking examples which underline the relevance of the topography of the charge distribution for the strength of the interatomic interactions; a The calculation of the atomic partial charges in (CO) 4Fe-BCp give a negative value of -0.56 e for Fe and a positive value of 0.32 e at B. Intuitively this could be interpreted as indication for strong ionic (electrostatic)Fe-B binding interactions. A more detailed bonding analysis suggests that there is indeed strong electrostatic attraction between Fe and B which arises, however, from the local negative charge concentration of the electron-lone pair at boron of the BCp donor ligand and the Fe nucleus. The (CO)4Fe metal fragment has an area of local charged depletion at Fe in the direction toward the BCp ligand: J. Uddin, G. Frenking, J. Am. Chem. Soc. 2001, 123, 1683;
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4Fe metal fragment has an area of local charged depletion at Fe in the direction toward the BCp ligand: J. Uddin, G. Frenking, J. Am. Chem. Soc. 2001, 123, 1683;
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22
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56349114749
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The bond dissociation energy and the intrinsic interaction energy between the frozen fragments of (CO)5M-PX3 shows that the M-P bonds of the halogen substituted systems with X=F, Cl are clearly weaker yet shorter than the M-P bonds when X=H, Me. A bonding analysis shows that the attractive orbital interactions in the former species are stronger than in the latter. The weaker bonding and shorter distances for the PF3 and PCl3 complexes come from the significantly smaller M-P electrostatic attraction which is caused by the much more compact electron lone-pair at phosphorous which overlaps much less with the metal nucleus than the electron lone-pair of the PH3 and PMe3 ligands: K. Wichmann, N. Fröhlich, J. Grobe, W. Golla, D. Le Van, B. Krebs, M. Läge, Organometallics 2002, 21, 2921
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3 ligands: K. Wichmann, N. Fröhlich, J. Grobe, W. Golla, D. Le Van, B. Krebs, M. Läge, Organometallics 2002, 21, 2921.
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24
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For a detailed discussion of the electronc structure and bonding situation in CO see
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For a detailed discussion of the electronc structure and bonding situation in CO see: G. Frenking, C. Loschen, A. Krapp, S. Fau, S. H. Strauss, J. Comput. Chem. 2007, 25, 117.
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(2007)
J. Comput. Chem
, vol.25
, pp. 117
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Frenking, G.1
Loschen, C.2
Krapp, A.3
Fau, S.4
Strauss, S.H.5
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