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Volumn 131, Issue 5, 2009, Pages 2029-2036

On the mechanism of B(C6F5)3-catalyzed direct hydrogenation of imines: Inherent and thermally induced frustration

Author keywords

[No Author keywords available]

Indexed keywords

AUTOCATALYTIC; CATALYTIC CYCLES; COMPLEX FORMS; DONOR-ACCEPTOR PAIRS; EXPERIMENTAL OBSERVATION; HYDROGEN SPLITTING; LEWIS ACID; LEWIS ACID-BASE; MECHANISTIC MODELS; NONCOVALENT ASSOCIATION; QUANTUM CHEMICAL CALCULATIONS; REACTION MECHANISM; SOLID SUPPORTS; THERMAL ACTIVATION; THERMALLY INDUCED;

EID: 67749129328     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja809125r     Document Type: Article
Times cited : (231)

References (103)
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    • On the reactant side of the TSs associated with H2 splitting, shallow minima can be identified corresponding to very weak ternary complexes; however, the reactions are suggested to be essentially bimolecular occurring upon the encounter of the frustrated complex and H2.
    • On the reactant side of the TSs associated with H2 splitting, shallow minima can be identified corresponding to very weak ternary complexes; however, the reactions are suggested to be essentially bimolecular occurring upon the encounter of the frustrated complex and H2.
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    • See the Supporting Information for details
    • See the Supporting Information for details.
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    • Sterically more crowded amines might not be able to quench the catalyst effectively
    • Sterically more crowded amines might not be able to quench the catalyst effectively.
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    • We have also considered the possibility of hydride attack to the unactivated imine and found this process to be thermodynamically unfavored. For instance, hydride transfer from[HB, to im is calculated to be endergonic by 73.8 kcal mol-1
    • -1.
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    • Due to the flexibility of the noncovalent complexes, r-am⋯B is supposed to easily isomerize to am ⋯ B without dissociation, thereby providing a shortcut from cycle 1 to cycle 2.
    • Due to the flexibility of the noncovalent complexes, r-am⋯B is supposed to easily isomerize to am ⋯ B without dissociation, thereby providing a shortcut from cycle 1 to cycle 2.
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