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Volumn 26, Issue 15, 2007, Pages 3651-3659

Computational studies on the stabilities of trans-[Ir(OMe)(CO)(PPh 3)2] and trans-[Ir(CH2Me)(CO)(PPh 3)2] toward β-H elimination

Author keywords

[No Author keywords available]

Indexed keywords

BINDING ENERGY; CHEMICAL STABILITY; DENSITY FUNCTIONAL THEORY; ISOMERIZATION; STEREOCHEMISTRY;

EID: 34547450618     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om700276p     Document Type: Article
Times cited : (21)

References (67)
  • 1
    • 3743092578 scopus 로고
    • For a review of low-valent transition metal alkoxide chemistry up to the late 1980s see
    • For a review of low-valent transition metal alkoxide chemistry up to the late 1980s see: Bryndza, H. E.; Tam, W. Chem. Rev. 1988, 88, 1163.
    • (1988) Chem. Rev , vol.88 , pp. 1163
    • Bryndza, H.E.1    Tam, W.2
  • 7
    • 24944468108 scopus 로고    scopus 로고
    • (b) Stahl, S. S. Science 2005, 309, 1824.
    • (2005) Science , vol.309 , pp. 1824
    • Stahl, S.S.1
  • 9
    • 34547411958 scopus 로고    scopus 로고
    • A variety of different mechanisms for the β-hydrogen elimination reactions of low-valent metal alkoxides have also been identified that would not necessarily be available for analogous alkyls. These include solventassisted methoxide dissociation followed by C-H bond activation6 as well as a binuclear decomposition pathway.7
    • 7
  • 19
  • 23
    • 2442596036 scopus 로고    scopus 로고
    • See also studies where the energetics of β-H transfer have been defined: (a) Huo, C.-F.; Li, Y.-W.; Beller, M.; Jiao, H. Organometallics 2004, 23, 2168.
    • See also studies where the energetics of β-H transfer have been defined: (a) Huo, C.-F.; Li, Y.-W.; Beller, M.; Jiao, H. Organometallics 2004, 23, 2168.
  • 25
    • 0030152598 scopus 로고    scopus 로고
    • + cation and entails a very high barrier of 37 kcal/mol. This was attributed to the high-spin state of the reactant (S = 5/2) and the consequent lack of vacant orbitais for interaction with the approaching C-H bond. Fiedler, A.; Schröder, D.; Schwarz, H.; Tjelta, B. L.; Armentrout, P. B. J. Am. Chem. Soc. 1996, 118, 5047.
    • + cation and entails a very high barrier of 37 kcal/mol. This was attributed to the high-spin state of the reactant (S = 5/2) and the consequent lack of vacant orbitais for interaction with the approaching C-H bond. Fiedler, A.; Schröder, D.; Schwarz, H.; Tjelta, B. L.; Armentrout, P. B. J. Am. Chem. Soc. 1996, 118, 5047.
  • 28
    • 0001146005 scopus 로고    scopus 로고
    • 2) and found each proceeded with similar small barriers of less than 2 kcal/mol. See: Versluis, L.; Ziegler, T.; Fan, L. Inorg. Chem. 1990, 29, 4530.
    • 2) and found each proceeded with similar small barriers of less than 2 kcal/mol. See: Versluis, L.; Ziegler, T.; Fan, L. Inorg. Chem. 1990, 29, 4530.
  • 29
    • 34547482439 scopus 로고    scopus 로고
    • Frisch, M.; et al. Gaussian 98, Revision A. 11.4; Gaussian, Inc.: Pittsburgh, PA, 2001.
    • Frisch, M.; et al. Gaussian 98, Revision A. 11.4; Gaussian, Inc.: Pittsburgh, PA, 2001.
  • 40
    • 34547439768 scopus 로고    scopus 로고
    • OMe are given as Supporting Information.
    • OMe are given as Supporting Information.
  • 41
    • 34547404698 scopus 로고    scopus 로고
    • 2 ligand moved out of the metal coordination plane is 23 kcal/mol higher in energy.
    • 2 ligand moved out of the metal coordination plane is 23 kcal/mol higher in energy.
  • 44
    • 34547418633 scopus 로고    scopus 로고
    • In principle, isomerization of TPH3 3a′ Et to TCO 3b′Et could occur, and a transition state for this process was located with a YEt geometry very similar to 2OMe- In this case, however, the inability of the Et ligand to act as a π-donor results in a very high energy, 39.8 kcal/mol and hence a very high barrier to isomerization. Moreover, subsequent β-H transfer in 3b′Et also has a larger barrier than that in 3a′Et, and so β-H elimination via 3a′Et will be favored on both counts. Full details of the formation and reactivity of 3b′Et are given in the Supporting Information
    • Et are given in the Supporting Information.
  • 45
    • 34547413419 scopus 로고    scopus 로고
    • OMe (AG = +2.7 kcal/mol).
    • OMe (AG = +2.7 kcal/mol).
  • 46
    • 34547472061 scopus 로고    scopus 로고
    • Attempts to compute this alternative η2-form showed that this species did not correspond to a local minimum, as all geometries converged on the more stable η1-isomer
    • 1-isomer.
  • 48
    • 84876688889 scopus 로고    scopus 로고
    • 1-Formaldehyde: W. Saak, W.; Pohl, S. Z. Anorg. Allg. Chem. 1987, 552, 186.
    • 1-Formaldehyde: W. Saak, W.; Pohl, S. Z. Anorg. Allg. Chem. 1987, 552, 186.
  • 49
    • 34547476589 scopus 로고    scopus 로고
    • 2-Formaldehyde: (a) Brown, K. L.; Clark, G. R.; Headford, C. E. L.; Marsden, K.; Roper, W. R. J. Am. Chem. Soc. 1982, 104, 2019.
    • 2-Formaldehyde: (a) Brown, K. L.; Clark, G. R.; Headford, C. E. L.; Marsden, K.; Roper, W. R. J. Am. Chem. Soc. 1982, 104, 2019.
  • 55
    • 34547460584 scopus 로고    scopus 로고
    • 1-Acetophenone: (a) Hevia, E.; Perez, J.; Riera, V.; Miguel, D.; Kassel, S.; Rheingold, A. Inorg. Chem. 2002, 41, 4671.
    • 1-Acetophenone: (a) Hevia, E.; Perez, J.; Riera, V.; Miguel, D.; Kassel, S.; Rheingold, A. Inorg. Chem. 2002, 41, 4671.
  • 63
    • 34547439767 scopus 로고    scopus 로고
    • Cadierno, V, Zablocka, M, Donnadieu, B, Igau, A, Majorai. J. P, Skowronska, A. Chem.-Eur. J. 2001, 7, 221. η2-Acetophenone: see ref 39
    • 2-Acetophenone: see ref 39.
  • 67
    • 34547414470 scopus 로고    scopus 로고
    • 3 ligands are in close contact. Vadivelu, P. Ph.D. Thesis, Heriot-Watt University, 2007.
    • 3 ligands are in close contact. Vadivelu, P. Ph.D. Thesis, Heriot-Watt University, 2007.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.