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Volumn 47, Issue 13, 2008, Pages 5910-5918

Computational analysis of amine-borane adducts as potential hydrogen storage materials with reversible hydrogen uptake

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EID: 47949122341     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic800344h     Document Type: Article
Times cited : (83)

References (88)
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    • For a discussion of a heterogeneous vs a homogeneous mechanism with Rh, see:(a) Jaska, C. A.; Manners, I. J. Am. Chem. Soc. 2004, 126, 1334.
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    • For a computational analysis of the thermal mechanism, see: d
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    • For a computational analysis of the mechanism using titanocene as the catalyst, see: f
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    • For a computational analysis of the mechanism using an Ir pincer complex as the catalyst, see: g
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    • For a computational analysis of the mechanism using a Ni carbene complex, see: h
    • For a computational analysis of the mechanism using a Ni carbene complex, see: (h) Yang, X.; Hall, M. B. J. Am. Chem. Soc. 2008, 130, 1798.
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    • Catalytic loss of dihydrogen from phosphine-borane adducts has been reported: (a) Dorn, H; Singh, R. A.; Massey, J. A.; Lough, A. J; Manners, I. Angew. Chem., Int. Ed. 1999, 38, 3321.
    • Catalytic loss of dihydrogen from phosphine-borane adducts has been reported: (a) Dorn, H; Singh, R. A.; Massey, J. A.; Lough, A. J; Manners, I. Angew. Chem., Int. Ed. 1999, 38, 3321.
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    • unpublished results
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    • For 6-31G, see: (a) Hehre, W. J.; Ditchfield, R.; Pople, J. A. J. Chem. Phys. 1972, 56, 2257.
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    • For 6-31G(d,p), see: (b) Hariharan, P. C.; Pople, J. A. Theor. Chim. Acta 1973, 28, 213.
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    • For the dehydrogenation of ethane, the thermodynamic parameters are ΔH = 32.7 kcal/mol, ΔS = 28.8 cal/(mol K) at 293.15 K, ΔG = 24.3 kcal/mol: Atkins, P.; de Paula, J. Atkins' Physical Chemistry; 7th ed.; Oxford University Press: New York, 2002.
    • For the dehydrogenation of ethane, the thermodynamic parameters are ΔH = 32.7 kcal/mol, ΔS = 28.8 cal/(mol K) at 293.15 K, ΔG = 24.3 kcal/mol: Atkins, P.; de Paula, J. Atkins' Physical Chemistry; 7th ed.; Oxford University Press: New York, 2002.
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    • For tables and figures of these quantities, see the Supporting Information
    • For tables and figures of these quantities, see the Supporting Information.
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    • For the calculation of the energy of the species involved, these authors use a process where the atomization energies are calculated and implemented together with known heats of formation of the relevant atoms to obtain the heats of formation at 0 K.
    • For the calculation of the energy of the species involved, these authors use a process where the atomization energies are calculated and implemented together with known heats of formation of the relevant atoms to obtain the heats of formation at 0 K.
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    • 5-containing compounds were not calculated due to their expense.
    • 5-containing compounds were not calculated due to their expense.
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    • For another computational study on bond dissociation enthalpies including some amine-boranes, see: a
    • For another computational study on bond dissociation enthalpies including some amine-boranes, see: (a) Jonas, V.; Frenking, G.; Reetz, M. T. J. Am. Chem. Soc. 1994, 116, 8741.
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    • 3 is under debate. While a commonly used explanation is that the Lewis acidity is a trade off between σ-withdrawing and π-donating effects, this has been contested by Frenking: (b) Bessac, F; Frenking, G
    • 3 is under debate. While a commonly used explanation is that the Lewis acidity is a trade off between σ-withdrawing and π-donating effects, this has been contested by Frenking: (b) Bessac, F; Frenking, G. Inorg. Chem. 2003, 42, 7990.
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    • This effect is less visible with the B3LYP calculations. Therefore, we repeated the calculations on the MP2/6-31G(d,p) level of theory for all compounds of the type X2NH-BH3 and H3N-BHX 2 with X, H, F, Cl, and Br and the corresponding dehydrogenated products. The results are given in the Supporting Information
    • 2 with X = H, F, Cl, and Br and the corresponding dehydrogenated products. The results are given in the Supporting Information.
  • 86
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    • We tested the possibility that HOTf may be preferentially released rather than hydrogen. We found that, thermodynamically, this is not expected
    • We tested the possibility that HOTf may be preferentially released rather than hydrogen. We found that, thermodynamically, this is not expected.
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    • It has been suggested that B3LYP may predict less exothermic reactions for dimerizations such as the ones described: Bissett, K. M, Gilbert, T. M. Organometallics 2004, 23, 850. However, this was shown for only one example
    • It has been suggested that B3LYP may predict less exothermic reactions for dimerizations such as the ones described: Bissett, K. M.; Gilbert, T. M. Organometallics 2004, 23, 850. However, this was shown for only one example.


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