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Volumn 26, Issue 14, 2007, Pages 3597-3600

Computational study of titanocene-catalyzed dehydrocoupling of the adduct Me2NH·BH3: An intramolecular, stepwise mechanism

Author keywords

[No Author keywords available]

Indexed keywords

CATALYST ACTIVITY; CROSSLINKING; DEHYDROGENATION; DENSITY FUNCTIONAL THEORY; ENERGY BARRIERS; MOLECULAR INTERACTIONS;

EID: 34547247600     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om7003892     Document Type: Article
Times cited : (100)

References (54)
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    • For the formation and usage of Ti(II) metallocenes, see: (a) Sato, F.; Urabe, H.; Okamoto, S. Chem. Rev. 2000, 100, 2835-2886.
    • For the formation and usage of Ti(II) metallocenes, see: (a) Sato, F.; Urabe, H.; Okamoto, S. Chem. Rev. 2000, 100, 2835-2886.
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    • For uncatalyzed dehydrogenations of ammonia-borane and hydrocarbon-borane, see: a
    • For uncatalyzed dehydrogenations of ammonia-borane and hydrocarbon-borane, see: (a) Glodfuss, B.; Knochel, P.; Bromm, L. O.; Knapp, K. Angew. Chem., Int. Ed. 2000, 39, 4136-4139.
    • (2000) Angew. Chem., Int. Ed , vol.39 , pp. 4136-4139
    • Glodfuss, B.1    Knochel, P.2    Bromm, L.O.3    Knapp, K.4
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    • The coordination via amine partner made the complex less stable by ∼5 kcal/mol compared to 1. From the point of view of the thermodynamics, we could not further investigate the reaction of such a less stable coordination complex. Although a complex coordinated in an η3 fashion via the B atom and two hydrogens of BH3 (see 1e in Figure S-3, Supporting Information) was computed to be more stable by 3.5 kcal/mol in comparison with 1, its dehydrogenated product via cleavage of a (μ2-H)-B bond was not computationally obtained see Figure S-4, Supporting Information, probably because it is hard for the μ2-H in the η3-coordinated complex to adopt the μ1 mode to bond to the Ti atom, when the partially dehydrogenated species H 2B-NHMe2 has no additional binding partner
    • 2 has no additional binding partner.
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    • Such a cyclic structure and the Ti·N and Ti·B interactions in TS[1-2] are suggested by the corresponding interatomic distances (see Table 1). These features of TS[1-2] can be also seen from the molecular orbital isosurface (see Figure S-11. Supporting Information).
    • Such a cyclic structure and the Ti·N and Ti·B interactions in TS[1-2] are suggested by the corresponding interatomic distances (see Table 1). These features of TS[1-2] can be also seen from the molecular orbital isosurface (see Figure S-11. Supporting Information).
  • 34
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    • During the reaction, the signal of a byproduct appeared and was tentatively assigned to the cyclic trimer [Me2N-BH2] 3. 4d As suggested in the same work, the cyclic trimer possibly resulted from the trimerization of 4, which should be less favorable than dimerization. We have also computationally found that the dissociation of this cyclic trimer leading to 5 and 4 is exergonic by 12.6 kcal/mol in solution, suggesting that the trimer can easily convert to the dimer 5. A small signal was also observed in the NMR spectrum during the reaction, which was assigned to the byproduct Me2N-BH-NMe 2. 4d Since the transformation shown in Scheme 1 is fully achieved, the reaction route leading to the Me2N-BH-NMe2 species is not preferred over path I (Scheme 2) and hence was not investigated in this study
    • 2 species is not preferred over path I (Scheme 2) and hence was not investigated in this study.
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    • The preference of the conversion of 1 to 2 over that of 6 to 7 is also suggested by the IRC following curves of TS[1-2] and TS[6-7] (see Figure S-7 and Figure S-9, Supporting Information).
    • The preference of the conversion of 1 to 2 over that of 6 to 7 is also suggested by the IRC following curves of TS[1-2] and TS[6-7] (see Figure S-7 and Figure S-9, Supporting Information).
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