Computational studies of structures and properties of metallaboranes. Part 3: Protonated iron bis(dicarbollide), [3-Fe-(1,2-C2B 9H11])2H-

Inorganic Chemistry

Volumn 46, Issue 5, 2007, Pages 1771-1777

  Bühl, Michael ^b   Hnyk, Drahomír ^a   Macháček, Jan ^a  

^a INSTITUTE OF INORGANIC CHEMISTRY   (Czech Republic)

^b MAX PLANCK INSTITUT FÜR KOHLENFORSCHUNG   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 33947409017     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic062096p     Document Type: Article

References (61)

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47. 11B chemical shifts are expected to be even smaller. There is thus no evidence for any "unbalance" in the basis sets that we are using.
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51. When optimizations of isomers of 2a-2c with a different location of the proton in the equatorial belt were attempted, rearrangements (dicarbollide rotations) occurred during minimization, affording the original or another variant of 2a-2c.
52. Stephan, M.; Davis, J. H., Jr.; Meng, X.; Chase, K. J.; Hauss, J.; Zenneck, U.; Pritzkow, H.; Siebert, W.; Grimes, R. N. J. Am. Chem. Soc. 1992, 114, 5214. This article also contains references to studies of other small metallcarboranes with this structural feature.
53. 6)H [optimized, Fe-H = 1.673 Å, mean = B-H 1.423 Å; observed for substituted derivative, Fe-H = 1.63(3) Å, B-H = 1.45(3) Å].
54. The same was found at the B3LYP/II′ level, where 2c is slightly more stable than 2b, by 0.2 kJ/mol.
55. The difference between TS2cc and TS2cc′ is that the latter scrambles, among others, only B4 with B4′ and B7 with B7′, whereas the former scrambles all four of these.
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57. 57Fe chemical shift has been reported; see: (a) Koridze, A. A.; Petrovskii, P. V.; Gubin, S. P.; Fedin, E. I. J. Organomet. Chem. 1975, 93, C26.
58. (b) Koridze, A. A.; Stakhova, N. M.; Petrovskii, P. V. J. Organomet. Chem. 1983, 254, 345.
59. An important reason for the stabilization of 2c over 2b in a polar environment is certainly the larger dipole moment of the former compared to that of the latter [4.8 D vs 2.6 D, respectively, at the BP86/AE1(*) level in vacuo; these values increase by ca. 70% each in solution]. Non-electrostatic contributions to the total free energy in solution (which are not included in the energies we report) are very similar for all isomers considered. It should be kept in mind that PCM approaches are very crude models that can, at best, describe long-range electrostatic interactions qualitatively, without accounting for specific solute-solvent interactions such as hydrogen bonds. We just note that the qualitative ordering of 2b and 2c as it emerges from the PCM data appears to be consistent with the results from the NMR computations.
60. It should be noted that the energetic difference between these isomers is also very small in the continuum, arguably within the accuracy of our computational level. In this case, discrimination via the chemical shifts is more reliable.
61. A good accord between computed and experimental chemical shifts cannot prove the correctness of the structure used in the computations, because the possibility cannot be excluded that two or more structures can show the same or very similar δ values. In that case, other criteria can be used to make a distinction, e.g., as in our case, relative energies. In contrast, a structure can be disproved in the case of a poor accord between theory and experiment, i.e., if it produces errors exceeding the usual accuracy of the computational method applied, as for 2b in our case