메뉴 건너뛰기




Volumn 47, Issue 13, 2008, Pages 2435-2438

Turning frustration into bond activation: A theoretical mechanistic study on heterolytic hydrogen splitting by frustrated Lewis pairs

Author keywords

Donor acceptor systems; Hydrogenation; Quantum chemistry; Reaction mechanisms

Indexed keywords

DONOR-ACCEPTOR SYSTEMS; HYDROGENATION; QUANTUM CHEMISTRY; REACTION MECHANISMS;

EID: 42449158036     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200705586     Document Type: Article
Times cited : (342)

References (36)
  • 11
    • 33751203567 scopus 로고    scopus 로고
    • a) G. J. Kubas, Science 2006, 314, 1096;
    • (2006) Science , vol.314 , pp. 1096
    • Kubas, G.J.1
  • 15
    • 33646469818 scopus 로고    scopus 로고
    • For a review paper and recent computational studies on the mechanism of metal-assisted heterolytic H-H activation, see: a G. J. Kubas, Adv. Inorg. Chem. 2004, 56, 127;
    • For a review paper and recent computational studies on the mechanism of metal-assisted heterolytic H-H activation, see: a) G. J. Kubas, Adv. Inorg. Chem. 2004, 56, 127;
  • 23
    • 53549124210 scopus 로고    scopus 로고
    • For computational details, see the Supporting Information
    • For computational details, see the Supporting Information.
  • 26
    • 53549132615 scopus 로고    scopus 로고
    • For details, see the Supporting Information
    • For details, see the Supporting Information.
  • 28
    • 53549092333 scopus 로고    scopus 로고
    • Our calculations carried out for the, tBu)3P] ⋯[B(C6H5)3] adduct underline the importance of C-H⋯F interactions to the bonding in, tBu) 3P]⋯[B(C6F5)3, but our results also indicate that their presence is not a prerequisite in the formation of frustrated complexes for details, see the Supporting Information
    • 3], but our results also indicate that their presence is not a prerequisite in the formation of frustrated complexes (for details, see the Supporting Information).
  • 29
    • 53549133745 scopus 로고    scopus 로고
    • The exothermicity of association is likely overcompensated by entropy loss, may not be obvious
    • 3] adducts may not be obvious.
    • 3] adducts
  • 30
    • 53549100559 scopus 로고    scopus 로고
    • Geometry optimization following initial IRC calculation leads to a very shallow energy minimum corresponding to a structure wherein H2 is weakly bound to an open form of the, tBu)3P]⋯[B(C 6F5)3] adduct; in the other direction, the, tBu)3PH][HB(C6F5)3] product is obtained see the Supporting Information
    • 3] product is obtained (see the Supporting Information).
  • 31
    • 0037167050 scopus 로고    scopus 로고
    • The TS we located bears common structural features with that identified by Chan and Radom for base-catalyzed hydrogenation of ketones. For detailed kinetic and computational studies, see: a A. Berkessel, T. J. S. Schubert, T. N. Müller, J. Am. Chem. Soc. 2002, 124, 8693;
    • The TS we located bears common structural features with that identified by Chan and Radom for base-catalyzed hydrogenation of ketones. For detailed kinetic and computational studies, see: a) A. Berkessel, T. J. S. Schubert, T. N. Müller, J. Am. Chem. Soc. 2002, 124, 8693;
  • 33
    • 53549098012 scopus 로고    scopus 로고
    • Δρ is defined as Δρ, ρ(TS)-ρ([(tBu) 3P]⋯[B(C6F5)3]*, ρ(H2*, where the atomic positions of, tBu) 3P]⋯[B(C6F5)3]* and H2* are identical to those in the TS
    • 2* are identical to those in the TS.
  • 34
    • 3042729899 scopus 로고    scopus 로고
    • The importance of the preorganization of active sites for an analogous near-linear four-centered TS has already been demonstrated in Rh-assisted homolytic H2 activation, albeit involving the intramolecular use of two metalloradical centers. See: W. Cui, B. B. Wayland, J. Am. Chem. Soc. 2004, 126, 8266
    • 2 activation, albeit involving the intramolecular use of two metalloradical centers. See: W. Cui, B. B. Wayland, J. Am. Chem. Soc. 2004, 126, 8266.
  • 35
    • 34250366259 scopus 로고    scopus 로고
    • The frustration energy can be quantified, for instance, by carrying out activation-strain analysis as proposed by Bickelhaupt and co-workers. See
    • The frustration energy can be quantified, for instance, by carrying out activation-strain analysis as proposed by Bickelhaupt and co-workers. See: G. T. de Jong, F. M. Bickelhaupt, ChemPhysChem 2007, 8, 1170.
    • (2007) ChemPhysChem , vol.8 , pp. 1170
    • de Jong, G.T.1    Bickelhaupt, F.M.2
  • 36
    • 53549130792 scopus 로고    scopus 로고
    • Frustrated complexes, C6H2Me3) 3P]⋯[B(C6F5)3] and, C 6F5)2B-C6F4-P(tBu) 2]⋯[(C6F5)2B-C 6F4-P(tBu)2] have also been identified in our calculations see the Supporting Information
    • 2] have also been identified in our calculations (see the Supporting Information).


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.