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Volumn 28, Issue 1, 2009, Pages 161-166

Elucidation of heterocumulene activation by a nucleophilic-at-metal iridium(I) carbene

Author keywords

[No Author keywords available]

Indexed keywords

ALKYLIDENES; ATOM TRANSFERS; BOND METATHESIS; CARBENE; CARBENE COMPLEXES; CARBENES; METAL CARBENES; METAL CENTERS; THEORETICAL STUDIES;

EID: 61849139983     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om8009766     Document Type: Article
Times cited : (31)

References (69)
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    • For leading references, see: a
    • For leading references, see: (a) Fischer, E. O. Pure Appl. Chem. 1970, 24, 407.
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  • 10
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    • Fischer Type Carbene Complexes
    • Beller, M, Bolm, C, Eds, Wiley-VCH: Weinheim
    • (j) Doetz, K. H.; Minatti, A. Fischer Type Carbene Complexes. In Transition Metals for Organic Synthesis; Beller, M., Bolm, C., Eds.; Wiley-VCH: Weinheim, 2004; Vol. 2, pp 397-425.
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    • Doetz, K.H.1    Minatti, A.2
  • 11
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    • Grubbs, R. H, Ed, Wiley-VCH: Weinheim
    • (k) Handbook of Metathesis; Grubbs, R. H., Ed.; Wiley-VCH: Weinheim, 2003.
    • (2003) Handbook of Metathesis
  • 24
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    • Examples of more commonly observed nucleophilic reactivity between metal carbenes and heterocumulenes: (a) Schrock, R. R. J. Am. Chem. Soc. 1976, 98, 5399
    • Examples of more commonly observed nucleophilic reactivity between metal carbenes and heterocumulenes: (a) Schrock, R. R. J. Am. Chem. Soc. 1976, 98, 5399.
  • 28
    • 29044433052 scopus 로고    scopus 로고
    • This behavior is more closely related to what is observed for Sadighi's structurally and electronically similar Cu(I)-boryl complexes: (a) Laitar, D. S, Müller, P, Sadighi, J. P. J. Am. Chem. Soc. 2005, 127, 17196
    • This behavior is more closely related to what is observed for Sadighi's structurally and electronically similar Cu(I)-boryl complexes: (a) Laitar, D. S.; Müller, P.; Sadighi, J. P. J. Am. Chem. Soc. 2005, 127, 17196.
  • 33
    • 0007887313 scopus 로고    scopus 로고
    • This binding motif for CS2 has been observed previously: (a) Werner, H, Kolb, O, Feser, R, Schubert, U. J. Organomet. Chem. 1980, 191, 283
    • 2 has been observed previously: (a) Werner, H.; Kolb, O.; Feser, R.; Schubert, U. J. Organomet. Chem. 1980, 191, 283.
  • 39
    • 0000493830 scopus 로고    scopus 로고
    • Though not observed for our system, an iridium-supported head-to-tail dimer of C02 has also been reported: Herskovitz, T, Guggenberger, L. J. J. Am. Chem. Soc. 1976, 98, 1615
    • 2 has also been reported: Herskovitz, T.; Guggenberger, L. J. J. Am. Chem. Soc. 1976, 98, 1615.
  • 40
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    • Similar behavior has been observed for phosphine-supported ruthenium carbenes: (a) Nguyen, S. T.; Johnson, L. K.; Grubbs, R. H.; Slier, J. W. J. Am. Chem. Soc. 1992, 113, 3974.
    • Similar behavior has been observed for phosphine-supported ruthenium carbenes: (a) Nguyen, S. T.; Johnson, L. K.; Grubbs, R. H.; Slier, J. W. J. Am. Chem. Soc. 1992, 113, 3974.
  • 49
    • 84868905713 scopus 로고    scopus 로고
    • 2 adduct and dithiolactone shown in Scheme 2 are in equilibrium, but we currently have no evidence supporting this view.
    • 2 adduct and dithiolactone shown in Scheme 2 are in equilibrium, but we currently have no evidence supporting this view.
  • 50
    • 33748245045 scopus 로고    scopus 로고
    • The reactivity of metal-ligand multiple bonds with carbon disulfide is typically initiated by nucleophilic ligands: (a) Mayr, A, Lee, T.-Y. Angew. Chem, Int. Ed. 1993, 32, 1726
    • The reactivity of metal-ligand multiple bonds with carbon disulfide is typically initiated by nucleophilic ligands: (a) Mayr, A.; Lee, T.-Y. Angew. Chem., Int. Ed. 1993, 32, 1726.
  • 52
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    • 8 metal complexes is well-known and has been extensively investigated: (a) Shriver, D. F
    • 8 metal complexes is well-known and has been extensively investigated: (a) Shriver, D. F. Ace. Chem. Res. 1970, 3, 231.
    • (1970) Ace. Chem. Res , vol.3 , pp. 231
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    • Further details regarding calculations on 1, 3, 5, and 6 are provided in the Supporting Information.
    • Further details regarding calculations on 1, 3, 5, and 6 are provided in the Supporting Information.
  • 59
    • 0001368552 scopus 로고
    • The electrophilicity of the metal center in many alkylidene complexes is so pronounced that the M=C-H bond angle is contracted to allow an a-agostic interaction with the electron-deficient metal center
    • (a) The electrophilicity of the metal center in many alkylidene complexes is so pronounced that the M=C-H bond angle is contracted to allow an a-agostic interaction with the electron-deficient metal center: Schultz, A. J.; Williams, J. M.; Schrock, R. R.; Rupprecht, G. A.; Fellmann, J. A. J. Am. Chem. Soc. 1979, 101, 1593.
    • (1979) J. Am. Chem. Soc , vol.101 , pp. 1593
    • Schultz, A.J.1    Williams, J.M.2    Schrock, R.R.3    Rupprecht, G.A.4    Fellmann, J.A.5
  • 63
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    • Schrodinger, LLC: New York, NY
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