Theoretical calculations of silica supported Mo2(η3-C3H5)4 species

Beulah Griffe; Anibal Sierraalta; Fernando Ruette; Joaquin L. Brito

doi:10.1016/S0166-1280(03)00011-3

Theoretical calculations of silica supported Mo₂(η³-C₃H₅)₄ species

Beulah Griffe
, Anibal Sierraalta
, Fernando Ruette
, Joaquin L. Brito

Instituto Venezolano de Investigaciones Científicas

Research output: Contribution to journal › Article › peer-review

8 Scopus citations

Abstract

Two models are studied for the anchored system Mo₂(η³-C ₃H₅)₄/SiO₂: united model (UM) and separated model (SM). Total energies, bond orders, diatomic energies, and parametric diatomic binding energies of selected bonds were calculated for Si₈O₂₄H₁₆, Mo₂(η³-C₃H₅)₄, and Mo₂(η³-C₃H₅) ₄/Si₈O₂₄H₁₆ systems, using a CNDO-UHF parametrical method. From the energetic viewpoint, UM is more stable than SM to explain the immobilizing of Mo₂(η³-C₃H₅)₄ on silica. It is observed Mo-H interaction that leads to C-H activation. These results support several features of the generally accepted mechanism for olefin metathesis. An interpretation of these theoretical results was carried by comparing with PAS-FTIR, ¹H and ¹³C solid-state NMR, and XPS trends.

Original language	English
Pages (from-to)	59-70
Number of pages	12
Journal	Journal of Molecular Structure: THEOCHEM
Volume	625
Issue number	1-3
DOIs	https://doi.org/10.1016/S0166-1280(03)00011-3
State	Published - 5 May 2003
Externally published	Yes

Keywords

Anchored complex
CNDO-UHF
Metathesis
Mo-allyl catalyst
Parametric method

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10.1016/S0166-1280(03)00011-3

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title = "Theoretical calculations of silica supported Mo2(η3-C3H5)4 species",

abstract = "Two models are studied for the anchored system Mo2(η3-C 3H5)4/SiO2: united model (UM) and separated model (SM). Total energies, bond orders, diatomic energies, and parametric diatomic binding energies of selected bonds were calculated for Si8O24H16, Mo2(η3-C3H5)4, and Mo2(η3-C3H5) 4/Si8O24H16 systems, using a CNDO-UHF parametrical method. From the energetic viewpoint, UM is more stable than SM to explain the immobilizing of Mo2(η3-C3H5)4 on silica. It is observed Mo-H interaction that leads to C-H activation. These results support several features of the generally accepted mechanism for olefin metathesis. An interpretation of these theoretical results was carried by comparing with PAS-FTIR, 1H and 13C solid-state NMR, and XPS trends.",

keywords = "Anchored complex, CNDO-UHF, Metathesis, Mo-allyl catalyst, Parametric method",

author = "Beulah Griffe and Anibal Sierraalta and Fernando Ruette and Brito, \{Joaquin L.\}",

year = "2003",

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doi = "10.1016/S0166-1280(03)00011-3",

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T1 - Theoretical calculations of silica supported Mo2(η3-C3H5)4 species

AU - Griffe, Beulah

AU - Sierraalta, Anibal

AU - Ruette, Fernando

AU - Brito, Joaquin L.

PY - 2003/5/5

Y1 - 2003/5/5

N2 - Two models are studied for the anchored system Mo2(η3-C 3H5)4/SiO2: united model (UM) and separated model (SM). Total energies, bond orders, diatomic energies, and parametric diatomic binding energies of selected bonds were calculated for Si8O24H16, Mo2(η3-C3H5)4, and Mo2(η3-C3H5) 4/Si8O24H16 systems, using a CNDO-UHF parametrical method. From the energetic viewpoint, UM is more stable than SM to explain the immobilizing of Mo2(η3-C3H5)4 on silica. It is observed Mo-H interaction that leads to C-H activation. These results support several features of the generally accepted mechanism for olefin metathesis. An interpretation of these theoretical results was carried by comparing with PAS-FTIR, 1H and 13C solid-state NMR, and XPS trends.

AB - Two models are studied for the anchored system Mo2(η3-C 3H5)4/SiO2: united model (UM) and separated model (SM). Total energies, bond orders, diatomic energies, and parametric diatomic binding energies of selected bonds were calculated for Si8O24H16, Mo2(η3-C3H5)4, and Mo2(η3-C3H5) 4/Si8O24H16 systems, using a CNDO-UHF parametrical method. From the energetic viewpoint, UM is more stable than SM to explain the immobilizing of Mo2(η3-C3H5)4 on silica. It is observed Mo-H interaction that leads to C-H activation. These results support several features of the generally accepted mechanism for olefin metathesis. An interpretation of these theoretical results was carried by comparing with PAS-FTIR, 1H and 13C solid-state NMR, and XPS trends.

KW - Anchored complex

KW - CNDO-UHF

KW - Metathesis

KW - Mo-allyl catalyst

KW - Parametric method

UR - https://www.scopus.com/pages/publications/0038372751

U2 - 10.1016/S0166-1280(03)00011-3

DO - 10.1016/S0166-1280(03)00011-3

M3 - Artículo

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SN - 0166-1280

VL - 625

SP - 59

EP - 70

JO - Journal of Molecular Structure: THEOCHEM

JF - Journal of Molecular Structure: THEOCHEM

IS - 1-3

ER -

Theoretical calculations of silica supported Mo₂(η³-C₃H₅)₄ species

Abstract

Keywords

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