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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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37
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33847802762
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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
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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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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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33751156972
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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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85034274453
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An intermolecular exchange cannot be absolutely discounted, but the kinetic inaccessibility of the fulvene α-H suggests that such a process is unlikely.
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85034305774
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note
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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.
-
-
-
-
77
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85034309640
-
-
note
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2)C-(Ph)=CPh) , see ref 26c.
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-
-
-
78
-
-
85034293595
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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
-
-
85034286529
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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
-
-
85034307908
-
-
note
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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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-
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81
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85034279295
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note
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Carmona proposes such a mechanism for the formation of an analogous iridapyrrole complex: see ref 23a.
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-
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83
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0000854947
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Buchanan, J. M.; Stryker, J. M.; Bergman, R. G. J. Am. Chem. Soc. 1986, 108, 1537.
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Buchanan, J.M.1
Stryker, J.M.2
Bergman, R.G.3
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84
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0000017810
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(a) Legzdins, P.; Rettig, S. J.; Sánchez, L. J.; Bursten, B. E.; Gatter, M. G. J. Am. Chem. Soc. 1985, 107, 1411.
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Legzdins, P.1
Rettig, S.J.2
Sánchez, L.J.3
Bursten, B.E.4
Gatter, M.G.5
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86
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0000202306
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(a) Legzdins, P.; Rettig, S. J.; Sánchez, L. J. Organometallics 1988, 7, 2394.
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(1988)
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Legzdins, P.1
Rettig, S.J.2
Sánchez, L.J.3
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88
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85034286343
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note
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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).
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-
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89
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0000917651
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(a) Kuzelka, J.; Legzdins, P.; Rettig, S. J.; Smith, K. M. Organometallics 1997, 16, 3569.
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Kuzelka, J.1
Legzdins, P.2
Rettig, S.J.3
Smith, K.M.4
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91
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0001079514
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Legzdins, P.; Rettig, S. J.; Ross, K. J.; Batchelor, R. J.; Einstein, F. W. B. Organometallics 1995, 14, 5579.
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(1995)
Organometallics
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Legzdins, P.1
Rettig, S.J.2
Ross, K.J.3
Batchelor, R.J.4
Einstein, F.W.B.5
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92
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0006131362
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X-ray Crystallographic Laboratory, Chemistry Department, The University of Minnesota: Minneapolis, MN
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Young, V. G., Jr., UNTWIN; X-ray Crystallographic Laboratory, Chemistry Department, The University of Minnesota: Minneapolis, MN, 1997.
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(1997)
UNTWIN
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Young Jr., V.G.1
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