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Volumn , Issue 16, 2008, Pages 2825-2835

Vanadium(I) chloride and lithium vanadium(I) dihydride as epimetallating reagents for unsaturated organic substrates: Constitution and mode of reaction

Author keywords

Epimetallation; EPR spectroscopy of VH2 ; Lithium vanadium(I) dihydride; Organic radical intermediates; Vanadium(I) chloride

Indexed keywords


EID: 53749096352     PISSN: 1434193X     EISSN: 10990690     Source Type: Journal    
DOI: 10.1002/ejoc.200800104     Document Type: Article
Times cited : (6)

References (35)
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    • The role of low-valent transition-metal salts in organic reductions has received abundant review: A) A. Fürstner
    • The role of low-valent transition-metal salts in organic reductions has received abundant review: a) A. Fürstner, Angew. Chem. Int. Ed. Engl. 1993, 32, 164;
    • (1993) Angew. Chem. Int. Ed. Engl , vol.32 , pp. 164
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    • A. Fürstner Ed, VCH, Weinheim
    • c) A. Fürstner (Ed.), Active Metals, VCH, Weinheim, 1996.
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    • For a review of the drawbacks and uncertainties inherent in such empirical procedures for generating subvalent, transitionmetal reductants, consult: J. J. Eisch, X. Shi, J. R. Alila, S. Thiele, Chem. Ber./Recueil 1997, 130, 1175-1187
    • For a review of the drawbacks and uncertainties inherent in such empirical procedures for generating subvalent, transitionmetal reductants, consult: J. J. Eisch, X. Shi, J. R. Alila, S. Thiele, Chem. Ber./Recueil 1997, 130, 1175-1187.
  • 20
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    • unpublished doctoral studies
    • J. J. Eisch, X. Shi, unpublished doctoral studies, 1996.
    • (1996)
    • Eisch, J.J.1    Shi, X.2
  • 23
    • 9444263106 scopus 로고    scopus 로고
    • For a recent authoritative review on applications of vanadium salts in organic synthesis, consult
    • For a recent authoritative review on applications of vanadium salts in organic synthesis, consult: T. Hirao, Chem. Rev. 1997, 97, 2707-2724.
    • (1997) Chem. Rev , vol.97 , pp. 2707-2724
    • Hirao, T.1
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    • The suggestion by a referee that metallic vanadium could be present in solid samples of 12 or 13 prior to gasometric protolyses is not supported by the following observations: all such treatments of samples of 12 or 13 with glacial acetic acid led rapidly to gas evolution and the formation of a clear green solution, with no suspended dark particles. In our experience with such protolyses that clearly have particulate metal (Ti, Zr, Hf, Cr and V), such metal remains unreacted after addition of HOAc.
    • The suggestion by a referee that metallic vanadium could be present in solid samples of 12 or 13 prior to gasometric protolyses is not supported by the following observations: all such treatments of samples of 12 or 13 with glacial acetic acid led rapidly to gas evolution and the formation of a clear green solution, with no suspended dark particles. In our experience with such protolyses that clearly have particulate metal (Ti, Zr, Hf, Cr and V), such metal remains unreacted after addition of HOAc.
  • 25
    • 53749090014 scopus 로고    scopus 로고
    • Although the by-product LiCl through its Cl- and the solvent THF may well be coordinated with 12 and/or 13 in solution, the gasometric protolysis of solid samples of 12 or 13 demonstrates that such solvated THF can be removed in high vacuum. As to chemical complexation of LiCl with samples of 12 and 13 in the solid state, such stable complexes are unlikely. In previous work, samples of TiCl 2·2THF, ZrCl2·2THF and LiCrH 2·2THF, free of LiCl, have been isolated from the solvent pair of THF and toluene, cf. ref.[8,13,19
    • [8,13,19]
  • 27
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    • G. Wilkinson, F. G. A. Stone, E. W. Abels Eds, Pergamon, New York
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    • (1982) Comprehensive Organometallic Chemistry I , vol.3 , pp. 647
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    • Consult the reference J. J. Eisch, J. N. Gitua, D. C. Doetschman, Eur. J. Inorg. Chem. 2006, 1968-1975, for the EPR studies on the open-chain biradical of the titanium(II) isopropoxide trimer and the probability that diamagnetic titanium(II) chloride also exists as a trimer in a corresponding three-membered ring.
    • Consult the reference J. J. Eisch, J. N. Gitua, D. C. Doetschman, Eur. J. Inorg. Chem. 2006, 1968-1975, for the EPR studies on the open-chain biradical of the titanium(II) isopropoxide trimer and the probability that diamagnetic titanium(II) chloride also exists as a trimer in a corresponding three-membered ring.
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    • 53749094381 scopus 로고    scopus 로고
    • 3 (octahedral) seems to be favorable here.
    • 3 (octahedral) seems to be favorable here.
  • 33
    • 53749093337 scopus 로고    scopus 로고
    • [1] [32] Detailed descriptions of appropriate techniques for working with air- and moisture-sensitive organometallics can be found in: J. J. Eisch, Organometallic Syntheses, 2, Academic Press, New York, 1981, pp. 1-84.
    • [1] [32] Detailed descriptions of appropriate techniques for working with air- and moisture-sensitive organometallics can be found in: J. J. Eisch, Organometallic Syntheses, vol. 2, Academic Press, New York, 1981, pp. 1-84.
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    • J. C. Pourhert, J. Behnke Eds, first edition, Aldrich Chemical Co, Milwaukee
    • 1H FT-NMR Spectra, vol. 1-2, first edition, Aldrich Chemical Co., Milwaukee, 1993.
    • (1993) 1H FT-NMR Spectra , vol.1-2
  • 35
    • 53749100374 scopus 로고
    • J. C. Pourhert, J. Behnke Eds, third edition, Aldrich Chemical Co, Milwaukee
    • 1H FT-NMR Spectra, third edition, Aldrich Chemical Co., Milwaukee, 1981.
    • (1981) 1H FT-NMR Spectra


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.