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Volumn 128, Issue 30, 2006, Pages 9651-9660

Mechanism of the aerobic oxidation of alcohols by palladium complexes of N-heterocyclic carbenes

Author keywords

[No Author keywords available]

Indexed keywords

CATALYST ACTIVITY; HYDRIDES; HYDROGEN; KINETIC THEORY; OXIDATION; OXYGEN; PALLADIUM; QUANTUM THEORY;

EID: 33746597447     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja060915z     Document Type: Article
Times cited : (78)

References (51)
  • 17
    • 33746596819 scopus 로고    scopus 로고
    • Also observed with 2-decanol
    • Also observed with 2-decanol.
  • 21
  • 37
    • 33746637392 scopus 로고    scopus 로고
    • note
    • We will use "reductive elimination" to describe the departure of acetic-acid from a Pd-hydride intermediate, although we feel this process is electronically closer to acid-base reactivity (a proton hopping from one pair of electrons on palladium to another on the free carboxylate oxygen) than to traditional reductive elimination (a single orbital changing in character from antibonding between two adjacent ligands to a metal lone-pair as the ligands form a bond).
  • 44
    • 33746633189 scopus 로고    scopus 로고
    • note
    • Due to their instability relative to preceding states, accumulation of 6 and 7 will be negligible.
  • 46
    • 33746584616 scopus 로고    scopus 로고
    • note
    • 1/2; i.e., barrier width is weighted more heavily than height.
  • 47
    • 33746600097 scopus 로고    scopus 로고
    • note
    • It may seem contradictory that there are three hydrogen-dominated modes in addition to the imaginary eigenvector. The motion along the reaction coordinate at TS2 is actually dominated by the ketone, as the O=C bond twists away from the Pd-H bond and a long hydrogen bond forms between a hydrogen on the substrate phenyl group and the free oxygen of the acetate ligand. The flatness of the PES near TS2 and the large mass of the ketone are responsible for the small magnitude of v‡.
  • 48
    • 33746603332 scopus 로고    scopus 로고
    • note
    • a, the assumption that liberated acid exists as dimers in solution does not affect these relations.
  • 51
    • 2442556459 scopus 로고    scopus 로고
    • Schrödinger, L.L.C., Portland, OR, 1991-2003
    • Jaguar 5.0; Schrödinger, L.L.C., Portland, OR, 1991-2003.
    • Jaguar 5.0


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.