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Alkyl Chain Growth on a Transition Metal Center: How Does Iron Compare to Ruthenium and Osmium?
Industrial Fischer-Tropsch processes involve the synthesis of hydrocarbons usually on metal surface catalysts. On the other hand, very few homogeneous catalysts are known to perform a Fischer-Tropsch style of reaction. In recent work, we established the catalytic properties of a diruthenium-platinum...
Autores principales: | , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
MDPI
2015
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4632703/ https://www.ncbi.nlm.nih.gov/pubmed/26426009 http://dx.doi.org/10.3390/ijms161023369 |
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author | Sainna, Mala A. de Visser, Sam P. |
author_facet | Sainna, Mala A. de Visser, Sam P. |
author_sort | Sainna, Mala A. |
collection | PubMed |
description | Industrial Fischer-Tropsch processes involve the synthesis of hydrocarbons usually on metal surface catalysts. On the other hand, very few homogeneous catalysts are known to perform a Fischer-Tropsch style of reaction. In recent work, we established the catalytic properties of a diruthenium-platinum carbene complex, [(CpRu)(2)(μ(2)-H)(μ(2)-NHCH(3))(μ(3)-C)PtCH(3)(P(CH(3))(3))(2)](CO)(n)(+) with n = 0, 2 and Cp = η(5)-C(5)(CH(3))(5), and showed it to react efficiently by initial hydrogen atom transfer followed by methyl transfer to form an alkyl chain on the Ru-center. In particular, the catalytic efficiency was shown to increase after the addition of two CO molecules. As such, this system could be viewed as a potential homogeneous Fischer-Tropsch catalyst. Herein, we have engineered the catalytic center of the catalyst and investigated the reactivity of trimetal carbene complexes of the same type using iron, ruthenium and osmium at the central metal scaffold. The work shows that the reactivity should increase from diosmium to diruthenium to diiron; however, a non-linear trend is observed due to multiple factors contributing to the individual barrier heights. We identified all individual components of these reaction steps in detail and established the difference in reactivity of the various complexes. |
format | Online Article Text |
id | pubmed-4632703 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2015 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
spelling | pubmed-46327032015-11-23 Alkyl Chain Growth on a Transition Metal Center: How Does Iron Compare to Ruthenium and Osmium? Sainna, Mala A. de Visser, Sam P. Int J Mol Sci Article Industrial Fischer-Tropsch processes involve the synthesis of hydrocarbons usually on metal surface catalysts. On the other hand, very few homogeneous catalysts are known to perform a Fischer-Tropsch style of reaction. In recent work, we established the catalytic properties of a diruthenium-platinum carbene complex, [(CpRu)(2)(μ(2)-H)(μ(2)-NHCH(3))(μ(3)-C)PtCH(3)(P(CH(3))(3))(2)](CO)(n)(+) with n = 0, 2 and Cp = η(5)-C(5)(CH(3))(5), and showed it to react efficiently by initial hydrogen atom transfer followed by methyl transfer to form an alkyl chain on the Ru-center. In particular, the catalytic efficiency was shown to increase after the addition of two CO molecules. As such, this system could be viewed as a potential homogeneous Fischer-Tropsch catalyst. Herein, we have engineered the catalytic center of the catalyst and investigated the reactivity of trimetal carbene complexes of the same type using iron, ruthenium and osmium at the central metal scaffold. The work shows that the reactivity should increase from diosmium to diruthenium to diiron; however, a non-linear trend is observed due to multiple factors contributing to the individual barrier heights. We identified all individual components of these reaction steps in detail and established the difference in reactivity of the various complexes. MDPI 2015-09-28 /pmc/articles/PMC4632703/ /pubmed/26426009 http://dx.doi.org/10.3390/ijms161023369 Text en © 2015 by the authors; licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution license (http://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Article Sainna, Mala A. de Visser, Sam P. Alkyl Chain Growth on a Transition Metal Center: How Does Iron Compare to Ruthenium and Osmium? |
title | Alkyl Chain Growth on a Transition Metal Center: How Does Iron Compare to Ruthenium and Osmium? |
title_full | Alkyl Chain Growth on a Transition Metal Center: How Does Iron Compare to Ruthenium and Osmium? |
title_fullStr | Alkyl Chain Growth on a Transition Metal Center: How Does Iron Compare to Ruthenium and Osmium? |
title_full_unstemmed | Alkyl Chain Growth on a Transition Metal Center: How Does Iron Compare to Ruthenium and Osmium? |
title_short | Alkyl Chain Growth on a Transition Metal Center: How Does Iron Compare to Ruthenium and Osmium? |
title_sort | alkyl chain growth on a transition metal center: how does iron compare to ruthenium and osmium? |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4632703/ https://www.ncbi.nlm.nih.gov/pubmed/26426009 http://dx.doi.org/10.3390/ijms161023369 |
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