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Volumn 118, Issue 24, 1996, Pages 5672-5683

Dissociative nucleophilic substitution of η2-olefin complexes via a novel η2-vinyl cation inTermediate

Author keywords

[No Author keywords available]

Indexed keywords

METAL COMPLEX;

EID: 0030018096     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja960389j     Document Type: Article
Times cited : (34)

References (56)
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    • For the general chemistry of transition metal-olefin complexes, see: (a) Collman, J. P.; Hegedus, L. S.; Norton, J. R.; Finke, R. G. Principles and Applications of Organotransition Metal Chemistry, 2nd ed.; University Science Books: Mill Valley, CA, 1987; Chapters 7-9, 16, 17. (b) Crabtree, R. H. The Organometallics Chemistry of the Transition Metals; John Wiley & Sons: New York, 1994; Chapters 5, 6, 11, 14. (c) Pearson A. J. Metallo-Organic Chemistry; John Wily & Sons: New York. 1985; Chapter 5.
    • (1994) The Organometallics Chemistry of the Transition Metals
    • Crabtree, R.H.1
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    • John Wily & Sons: New York. Chapter 5
    • For the general chemistry of transition metal-olefin complexes, see: (a) Collman, J. P.; Hegedus, L. S.; Norton, J. R.; Finke, R. G. Principles and Applications of Organotransition Metal Chemistry, 2nd ed.; University Science Books: Mill Valley, CA, 1987; Chapters 7-9, 16, 17. (b) Crabtree, R. H. The Organometallics Chemistry of the Transition Metals; John Wiley & Sons: New York, 1994; Chapters 5, 6, 11, 14. (c) Pearson A. J. Metallo-Organic Chemistry; John Wily & Sons: New York. 1985; Chapter 5.
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    • note
    • w = 0.067) for 1967 absorption-corrected reflections with I > 3σ(I). Unresolvable disorder of the organic ligand prevented any detailed analysis of its geometry.
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    • note
    • The assignments of the coordinated carbons α or β to the oxygenated substituent were determined through DEPT experiments, and the assignments for the respective protons were confirmed by proton-proton decoupling and HETCOR procedures.
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    • Theoretical calculations and experimental findings (synthesis of optically active sulfonium salt, and their crystal structure data) both confirm a pyramidal conformation for sulfonium salt. The barrier for inversion is calculated to be 24 kcal/mol with d orbitals and 13.5 kcal/mol without d orbitals. See: (a) Simonetta, M.; Gavezzotti, A. In The Chemistry of the Sulphonium Group; Stirling, C. J. M., Ed.; J. Wiley & Sons: New York, 1981; Part 1, Chapter 1, pp 1-14. (b) Andersen, K. K. Ibid.; Chapter 10.
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    • Chapter 10
    • Theoretical calculations and experimental findings (synthesis of optically active sulfonium salt, and their crystal structure data) both confirm a pyramidal conformation for sulfonium salt. The barrier for inversion is calculated to be 24 kcal/mol with d orbitals and 13.5 kcal/mol without d orbitals. See: (a) Simonetta, M.; Gavezzotti, A. In The Chemistry of the Sulphonium Group; Stirling, C. J. M., Ed.; J. Wiley & Sons: New York, 1981; Part 1, Chapter 1, pp 1-14. (b) Andersen, K. K. Ibid.; Chapter 10.
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    • note
    • This method of preparation for the vinylpyridinium complex 19 was found to be inferior to that reported in the Experimental Section.
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    • note
    • π-bound olefin, ketone, and iminium complexes of pentaammineosmium(II) in every case documented show cis- and trans-ammine resonances separated by > 1 ppm.
  • 27
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    • note
    • 2-vinylacetate complex 14 with neat HOTf.
  • 28
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    • note
    • CH = 7.9 Hz.
  • 37
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    • note
    • HH = 10.7 Hz).
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    • (a) For a review of the formation of carbyne complexes involving α,β-migration of hydrogen in a vinyl ligand, see: Mayr, A.; Hoffmeister, H. Adv. Organomet. Chem. 1991, 32, 251. (b) Bottrill, M.; Green, M. J. Am. Chem. Soc. 1977, 99, 5795. (c) Allen, S. R.; Beevor, R. G.: Green, M.; Orpen, A. G.; Paddick, K. E.; Williams, I. D. J. Chem. Soc., Dalton Trans. 1987, 591. (d) Atagi, L. M.; Mayer, J. M. Polyhedron 1995, 14 (1), 113.
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    • (a) For a review of the formation of carbyne complexes involving α,β-migration of hydrogen in a vinyl ligand, see: Mayr, A.; Hoffmeister, H. Adv. Organomet. Chem. 1991, 32, 251. (b) Bottrill, M.; Green, M. J. Am. Chem. Soc. 1977, 99, 5795. (c) Allen, S. R.; Beevor, R. G.: Green, M.; Orpen, A. G.; Paddick, K. E.; Williams, I. D. J. Chem. Soc., Dalton Trans. 1987, 591. (d) Atagi, L. M.; Mayer, J. M. Polyhedron 1995, 14 (1), 113.
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    • (a) For a review of the formation of carbyne complexes involving α,β-migration of hydrogen in a vinyl ligand, see: Mayr, A.; Hoffmeister, H. Adv. Organomet. Chem. 1991, 32, 251. (b) Bottrill, M.; Green, M. J. Am. Chem. Soc. 1977, 99, 5795. (c) Allen, S. R.; Beevor, R. G.: Green, M.; Orpen, A. G.; Paddick, K. E.; Williams, I. D. J. Chem. Soc., Dalton Trans. 1987, 591. (d) Atagi, L. M.; Mayer, J. M. Polyhedron 1995, 14 (1), 113.
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    • note
    • 2-allene from 33 resulted in intractable mixtures.


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