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Theoretical investigation of the first-shell mechanism of acetylene hydration catalyzed by a biomimetic tungsten complex

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Abstract

The reaction mechanism of the hydration of acetylene to acetaldehyde catalyzed by [WIVO(mnt)2]2− (where mnt2− is 1,2-dicyanoethylenedithiolate) is studied using density functional theory. Both the uncatalyzed and the catalyzed reaction are considered to find out the origin of the catalysis. Three different models are investigated, in which an aquo, a hydroxo, or an oxo coordinates to the tungsten center. A first-shell mechanism is suggested, similarly to recent calculations on tungsten-dependent acetylene hydratase. The acetylene substrate first coordinates to the tungsten center in an η2 fashion. Then, the tungsten-bound hydroxide activates a water molecule to perform a nucleophilic attack on the acetylene, resulting in the formation of a vinyl anion and a tungsten-bound water molecule. This is followed by proton transfer from the tungsten-bound water molecule to the newly formed vinyl anion intermediate. Tungsten is directly involved in the reaction by binding and activating acetylene and providing electrostatic stabilization to the transition states and intermediates. Three other mechanisms are also considered, but the associated energetic barriers were found to be very high, ruling out those possibilities.

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Acknowledgments

We gratefully acknowledge Margareta Blomberg (Stockholm University) for her critical comments on this manuscript. We appreciate Sven de Marothy (Stockholm University) providing the XYZ viewer which helped us to create all the figures of the molecule models. This work was supported by grants from the National Natural Science Foundation of China (grants 20573011, 20733002, and 20873008) and Major State Basic Research Development Programs (grant 2004CB719903).

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Authors and Affiliations

  1. College of Chemistry, Beijing Normal University, Beijing, 100875, People’s Republic of China

    Yan-Fang Liu, Rong-Zhen Liao, Wan-Jian Ding, Jian-Guo Yu & Ruo-Zhuang Liu

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  1. Yan-Fang Liu
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  2. Rong-Zhen Liao
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  3. Wan-Jian Ding
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  5. Ruo-Zhuang Liu
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Correspondence to Jian-Guo Yu.

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Liu, YF., Liao, RZ., Ding, WJ. et al. Theoretical investigation of the first-shell mechanism of acetylene hydration catalyzed by a biomimetic tungsten complex. J Biol Inorg Chem 16, 745–752 (2011). https://doi.org/10.1007/s00775-011-0775-x

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  • DOI: https://doi.org/10.1007/s00775-011-0775-x

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