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The Organometallic Chemistry of Carbon Dioxide Pertinent to Catalysis

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Enzymatic and Model Carboxylation and Reduction Reactions for Carbon Dioxide Utilization

Part of the book series: NATO ASI Series ((ASIC,volume 314))

Abstract

The mechanistic aspects of the C-X bond forming reactions resulting from CO2 insertion into M-X bonds, where X = H, R, OR, and NR2, must be elaborated if we are to be successful in developing catalysts for processes leading to useful chemicals derived from carbon dioxide. Of the three reactions involving the coupling of CO2 with coordinated ligands (M-H, M-R, M-OR) which are of primary interest in our research, only the C-C bond formation process is generally irreversible.

Our present understanding of the mechanism of the carbon-carbon bond forming process is the most detailed. Since carbon dioxide insertion into anionic metal-hydrides and metal-alkoxides is often a rapid process, limited mechanistic information for these processes is available. In contrast, the reverse process, decarboxylation, generally occurs on a timescale which is amenable to kinetic analysis by isotopic labelling experiments such as depicted in the equation below.

$$ M - OC(O)H + *C{{O}_{2}} \to M - O*C(O)H + C{{O}_{2}} $$

The mechanistic view emerging from these studies is that the decarboxylation reaction is strongly dependent on the nature of the X group in the [MOC(O)X] moiety. That is, the X group must have an appropriate orbital for interaction with the metal center during the decarboxylation process. This in turn requires significant interaction between CO2 and X group during the C-X bond forming reaction. A detailed analysis of the carboxylation/decarboxylation pathways will be presented. These insertion reactions can play pivotal roles in the mechanisms of the syntheses of organic products from carbon dioxide. Such processes include the production of alkyl formates, carboxylic acids, lactones, alkylpolycarbonates, etc.

Finally, the utilization of organometallic chemistry to develop better heterogeneous metal catalysts for the production of chemical feedstocks from CO2, e.g. CH4 and CH3OH, will be discussed. One of the essential problems to be dealt with in heterogeneous catalysts is the preparation and stabilization of very small metal particles supported on oxide carriers. In this regard metal carbonyl clusters in and on solid metal supports such as silica, alumina, and magnesia, serve as good sources of highly dispersed, low-valent metals for catalysis. Our efforts in the area of CO2 methanation employing ruthenium carbonyl clusters on alumina and in zeolite supercages will be summarized.

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Authors and Affiliations

  1. Department of Chemistry, Texas A&M University, College Station, Texas, 77843, USA

    Donald J. Darensbourg

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  1. Donald J. Darensbourg
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Editors and Affiliations

  1. Department of Chemistry, University of Bari, Bari, Italy

    M. Aresta

  2. Central Research & Development Department, E.I. du Pont de Nemours & Co., Wilmington, Delaware, USA

    J. V. Schloss

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© 1990 Kluwer Academic Publishers

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Darensbourg, D.J. (1990). The Organometallic Chemistry of Carbon Dioxide Pertinent to Catalysis. In: Aresta, M., Schloss, J.V. (eds) Enzymatic and Model Carboxylation and Reduction Reactions for Carbon Dioxide Utilization. NATO ASI Series, vol 314. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-0663-1_4

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  • DOI: https://doi.org/10.1007/978-94-009-0663-1_4

  • Publisher Name: Springer, Dordrecht

  • Print ISBN: 978-94-010-6783-6

  • Online ISBN: 978-94-009-0663-1

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