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Chromium tricarbonyl complexes of 1,2-and 1,4-dihydronaphthalene. Synthesis and metal-induced thermal isomerizations involving endo-hydrogen atoms

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Abstract

Reactions of 1,4-dihydronaphthalene with (NH3)3Cr(CO)3 or Py3Cr(CO)3 in the presence of BF3·Et2O afford a mixture of isomeric η6-chromium tricarbonyl complexes of 1,4-and 1,2-dihydronaphthalene in the ratio 63: 37 and 55: 45, respectively. The complexes were separated by chromatography. At 130 °C in different solvents these complexes undergo thermally induced reversible rearrangement studied by the 2H NMR method for the deuterated derivatives. Analysis of the 2H NMR spectra showed that the isomerization occurs due to metal-induced 1,5-shifts of the endo-hydrogen atoms. The isomerization mechanism was studied by quantum chemical DFT calculations. The calculations showed that the process occurs with the maximum activation barrier (33.2 kcal mol−1) through a series of agostic and hydride intermediates and transition states in which the chromium atom stereospecifically activates the endo-hydrogen atoms only.

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Authors and Affiliations

  1. Department of Chemistry, M. V. Lomonosov Moscow State University, 1 Leninskie Gory, 119992, Moscow, Russian Federation

    Yu. F. Oprunenko, I. P. Gloriozov & D. A. Lemenovskii

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  1. Yu. F. Oprunenko
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  2. I. P. Gloriozov
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  3. D. A. Lemenovskii
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Correspondence to Yu. F. Oprunenko.

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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 235–246, February, 2007.

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Oprunenko, Y.F., Gloriozov, I.P. & Lemenovskii, D.A. Chromium tricarbonyl complexes of 1,2-and 1,4-dihydronaphthalene. Synthesis and metal-induced thermal isomerizations involving endo-hydrogen atoms. Russ Chem Bull 56, 242–254 (2007). https://doi.org/10.1007/s11172-007-0040-1

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  • DOI: https://doi.org/10.1007/s11172-007-0040-1

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