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The activation of C-H bonds in C1-C3 alkanes by zirconium(III,IV) and titanium(III,IV) hydrides immobilized on the surface of SiO2: a density functional theory study

  • Structure of Matter and Quantum Chemistry
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Abstract

Model reactions of the (≡Si-O-)3MIVH (1), (≡Si-O-)2MIVH2 (2), and (≡Si-O-)2MIIIH (3) hydrides, where M = Ti and Zr, immobilized on the surface of silica with methane and propane were studied by the density functional theory with the PBE functional. The reactions involved the breaking of C-H alkane bonds and the formation of the (≡Si-O-)3MR, (≡Si-O-)2M(H)R, and (≡Si-O-)2MR products (R = Me, n-Pr, and i-Pr), respectively. Reactions with the participation of 1 and 2 were found to occur as bimolecular processes without the formation of agostic-type prereaction complexes. With 3, the reaction was accompanied by the formation of stable prereaction and postreaction complexes. The conclusion was drawn that dihydrides 2 and trivalent metal hydrides 3 were much more reactive with respect to alkane C-H bonds than monohydrides 1. All the systems studied were characterized by low reaction regioselectivities.

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Authors and Affiliations

  1. Faculty of Chemistry, Moscow State University, Leninskie gory, Moscow, 119992, Russia

    L. Yu. Ustynyuk, I. A. Aleshkin, Yu. V. Suleimanov, D. V. Besedin, Yu. A. Ustynyuk & V. V. Lunin

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  1. L. Yu. Ustynyuk
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  2. I. A. Aleshkin
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  3. Yu. V. Suleimanov
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  4. D. V. Besedin
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  5. Yu. A. Ustynyuk
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  6. V. V. Lunin
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Original Russian Text © L.Yu. Ustynyuk, I.A. Aleshkin, Yu.V. Suleimanov, D.V. Besedin, Yu.A. Ustynyuk, V.V. Lunin, 2007, published in Zhurnal Fizicheskoi Khimii, 2007, Vol. 81, No. 5, pp. 869–876.

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Ustynyuk, L.Y., Aleshkin, I.A., Suleimanov, Y.V. et al. The activation of C-H bonds in C1-C3 alkanes by zirconium(III,IV) and titanium(III,IV) hydrides immobilized on the surface of SiO2: a density functional theory study. Russ. J. Phys. Chem. 81, 752–758 (2007). https://doi.org/10.1134/S0036024407050184

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  • DOI: https://doi.org/10.1134/S0036024407050184

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