The origin of the remarkable regioselectivity of fe+-mediated dehydrogenation in benzocycloalkenes

Chemistry - A European Journal

Volumn 3, Issue 8, 1997, Pages 1315-1323

  Hertwig, Roland H ^a   Seemeyer, Katrin ^a   Schwarz, Helmut ^a   Koch, Wolfram ^a  

^a TECHNISCHE UNIVERSITÄT BERLIN   (Germany)

Author keywords

C H activation; Density functional calculations; Gas phase chemistry; Mass spectrometry; Transition metals

Indexed keywords

EID: 0030864679     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/chem.19970030819     Document Type: Article

References (53)

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48. An approximate optimization procedure, in which the coordinates of the five-membered transition-state structural element were kept frozen while the rest of the molecule was optimized, was not found to be successful, since only the coordinates of the transition-state structural element (i.e. those shown in Figure 3, Table 2) are known from the model study. Other geometrical parameters which would also have to be kept frozen in such a restricted optimization, such as the distance between the iron cation and the benzenoid moiety of the molecule, are not known a priori. However, this distance is decisive in determining the relative energy of the structure. Therefore, we deemed it necessary to completely optimize the geometries of all transition-state structures.
49. One of the reviewers pointed out that through ring slippage reactions the benzenoid part could loose its planarity upon change of hapticity of the metalbenzene bond, as found by J. M. O'Conner, C. P. Casey, Chem. Rev. 1987, 87, 307 and T. G. Traylor, K. J. Stewart, J. Am. Chem. Soc. 1986, 108, 6977. Such a distortion of the aromatic unit was, however, not found in the present calculations even though the benzene ring was not forced to maintain its planarity.
50. One of the reviewers pointed out that through ring slippage reactions the benzenoid part could loose its planarity upon change of hapticity of the metalbenzene bond, as found by J. M. O'Conner, C. P. Casey, Chem. Rev. 1987, 87, 307 and T. G. Traylor, K. J. Stewart, J. Am. Chem. Soc. 1986, 108, 6977. Such a distortion of the aromatic unit was, however, not found in the present calculations even though the benzene ring was not forced to maintain its planarity.
51. R. H. Hertwig, W. Koch, unpublished results.
52. 10-12, probably owing to weak interactions between the iron cation and the benzenoid substructure.
53. 10-12 have been checked; however, a saddle point could not be located in any other case.