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Volumn 17, Issue 5, 1998, Pages 854-871

Ligand elaboration mediated by a Cp*W(NO) template: Stepwise incorporation of small molecules into a tungsten vinyl fragment

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EID: 0000356684     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om971080r     Document Type: Article
Times cited : (41)

References (92)
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    • This field has been reviewed extensively, see, for example: (a) Vollhardt, K. P. C. Acc. Chem. Res. 1977, 10, 1. (b) Buchwald, S. L.; Nielsen, R. B. Chem. Rev. 1988, 88, 1047. (c) Carnahan, E. M.; Protasiewicz, J. D.; Lippard, S. J. Acc. Chem. Res. 1993, 26, 90. (d) Broene, R. D.; Buchwald, S. L. Science 1993, 261, 1696. (e) Negishi, E.-I.; Takahashi, T. Acc. Chem. Res. 1994, 27, 124.
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    • This field has been reviewed extensively, see, for example: (a) Vollhardt, K. P. C. Acc. Chem. Res. 1977, 10, 1. (b) Buchwald, S. L.; Nielsen, R. B. Chem. Rev. 1988, 88, 1047. (c) Carnahan, E. M.; Protasiewicz, J. D.; Lippard, S. J. Acc. Chem. Res. 1993, 26, 90. (d) Broene, R. D.; Buchwald, S. L. Science 1993, 261, 1696. (e) Negishi, E.-I.; Takahashi, T. Acc. Chem. Res. 1994, 27, 124.
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    • This field has been reviewed extensively, see, for example: (a) Vollhardt, K. P. C. Acc. Chem. Res. 1977, 10, 1. (b) Buchwald, S. L.; Nielsen, R. B. Chem. Rev. 1988, 88, 1047. (c) Carnahan, E. M.; Protasiewicz, J. D.; Lippard, S. J. Acc. Chem. Res. 1993, 26, 90. (d) Broene, R. D.; Buchwald, S. L. Science 1993, 261, 1696. (e) Negishi, E.-I.; Takahashi, T. Acc. Chem. Res. 1994, 27, 124.
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    • A recent theoretical analysis describes ring strain and bond enthalpies as the major contributors to the stability of methylcyclopropane relative to methylcyclopropene, see: Johnson, W. T. G.; Borden, W. T. J. Am. Chem. Soc. 1997, 119, 5930.
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    • For other examples of ketone-stabilized vinyl complexes, see: (a) Alt, H. G.; Eichner, M. E.; Jansen, B. M. Angew. Chem., Int. Ed. Engl. 1982, 21, 861. (b) Alt, H. G.; Hayen, H. I. J. Organomet. Chem. 1986, 103, 1501. (c) Bianchini, C.; Innocenti, P.; Melli, A.; Sabat, M. Organometallics 1986, 5, 72. (d) Reference 10.
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    • For other examples of ketone-stabilized vinyl complexes, see: (a) Alt, H. G.; Eichner, M. E.; Jansen, B. M. Angew. Chem., Int. Ed. Engl. 1982, 21, 861. (b) Alt, H. G.; Hayen, H. I. J. Organomet. Chem. 1986, 103, 1501. (c) Bianchini, C.; Innocenti, P.; Melli, A.; Sabat, M. Organometallics 1986, 5, 72. (d) Reference 10.
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    • For other examples of ketone-stabilized vinyl complexes, see: (a) Alt, H. G.; Eichner, M. E.; Jansen, B. M. Angew. Chem., Int. Ed. Engl. 1982, 21, 861. (b) Alt, H. G.; Hayen, H. I. J. Organomet. Chem. 1986, 103, 1501. (c) Bianchini, C.; Innocenti, P.; Melli, A.; Sabat, M. Organometallics 1986, 5, 72. (d) Reference 10.
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    • Reference 10
    • For other examples of ketone-stabilized vinyl complexes, see: (a) Alt, H. G.; Eichner, M. E.; Jansen, B. M. Angew. Chem., Int. Ed. Engl. 1982, 21, 861. (b) Alt, H. G.; Hayen, H. I. J. Organomet. Chem. 1986, 103, 1501. (c) Bianchini, C.; Innocenti, P.; Melli, A.; Sabat, M. Organometallics 1986, 5, 72. (d) Reference 10.
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    • 3- has Mo=O = 1.697(7) Å and Mo-OH = 2.077(7) Å; see: Robinson, P. R.; Schlemper, E. O.; Murmann, R. K. Inorg. Chem. 1975, 14, 2035. Typical terminal W-oxo bond distances lie in the range 1.68-1.72 Å, see: Nugent, W. A.; Mayer, J. M. Metal Ligand Multiple Bonds; Wiley: New York, 1988.
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    • Wiley: New York
    • 3- has Mo=O = 1.697(7) Å and Mo-OH = 2.077(7) Å; see: Robinson, P. R.; Schlemper, E. O.; Murmann, R. K. Inorg. Chem. 1975, 14, 2035. Typical terminal W-oxo bond distances lie in the range 1.68-1.72 Å, see: Nugent, W. A.; Mayer, J. M. Metal Ligand Multiple Bonds; Wiley: New York, 1988.
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    • Aromaticity has been invoked for similar aza- and thiapentadienyl iridium systems, see: (a) Alvarado, Y.; Daff, P. J.; Pérez, P. J.; Poveda, M. L.; Sánchez-Delgado, R.; Carmona, E. Organometallics 1996, 15, 2192. (b) Bleeke, J. R.; Ontwerth, M. F.; Rohde, A. M. Organometallics 1995, 14, 2813.
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    • Reference 23a
    • (f) Reference 23a.
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    • note
    • An intermolecular exchange cannot be absolutely discounted, but the kinetic inaccessibility of the fulvene α-H suggests that such a process is unlikely.
  • 76
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    • note
    • The formal 1,5-tautomerization can also be viewed as two sequential 1,3-H shifts; the first transfer occurs from the methyl group to the internal imine N and the second from the internal imine N to the terminal amide N. That the tautomerization is shown to be intermolecular renders these labels formal descriptors only.
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    • note
    • 2)C-(Ph)=CPh) , see ref 26c.
  • 78
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    • note
    • The results of this crossover experiment only confirm the intermolecular component to this tautomerization. An intramolecular component cannot be ruled out in the absence of the appropriate kinetic studies.
  • 79
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    • note
    • A very rapid isomerization (on the NMR time scale) between Y and 11 cannot be discounted from the experimental data.
  • 80
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    • note
    • A manuscript describing the scope of the thermal C-H activation chemistry observed for this system in the presence of a variety of hydrocarbons, including a detailed kinetic and mechanistic analysis, is currently in preparation.
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    • note
    • Carmona proposes such a mechanism for the formation of an analogous iridapyrrole complex: see ref 23a.
  • 88
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    • note
    • The other three lobes of the LUMO are kinetically inaccessible. One of the three extends upwards toward the Cp* ring, whereas access to the other two lobes is presumably blocked by the Cp* methyl substituents (which have been omitted for clarity in Figure 9).
  • 92
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    • X-ray Crystallographic Laboratory, Chemistry Department, The University of Minnesota: Minneapolis, MN
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