Mechanism of Ethylene Addition to Nickel Bis(oxothiolene) and Nickel Bis(dioxolene) Complexes
The electrochemically reversible binding of olefins by nickel bis(dithiolene) has been extensively studied, both theoretically and computationally. To optimize a catalyst for this process, we have investigated all possible reaction pathways of ethylene addition onto the related complex nickel bis(dioxolene), and the two isomers (cis and trans) of nickel bis(oxothiolene). Modern DFT calculations predict that the nickel bis(dioxolene) complex has limited practical use due to high barriers to binding. However, each of the two isomers of the nickel bis(oxothiolene) complexes display enhanced properties versus the original nickel bis(dithiolene) complex. Specifically, in nickel bis(dithiolene), the intraligand binding of olefins leads to decomposition, whereas interligand binding is required for reversibility; the two nickel bis(oxothiolene) complexes have greater selectivity toward the formation of the desired interligand adducts. For the full reaction pathways, the new complexes’ binding mechanisms are contrasted with the mechanism of the original catalyst.
This article is cited by 5 publications.
- Dušan N. Sredojević, Salvador Moncho, Rajesh Kumar Raju, Milivoj R. Belić, Edward N. Brothers. Reversible Olefin Addition to Extended Lattices of a Nickel–Selenium Framework. The Journal of Physical Chemistry C 2018, 122
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- Jayaraman Pitchaimani, Shao-Fei Ni, Li Dang. Metal dithiolene complexes in olefin addition and purification, small molecule adsorption, H2 evolution and CO2 reduction. Coordination Chemistry Reviews 2020, 420 , 213398. https://doi.org/10.1016/j.ccr.2020.213398
- Dušan N. Sredojević, Rajesh K. Raju, Salvador Moncho, Milivoj R. Belić, Edward N. Brothers. Computational investigation of cobalt and copper bis (oxothiolene) complexes as an alternative for olefin purification. Journal of Molecular Modeling 2020, 26
- Mohamed F. Shibl, Salvador Moncho, Edward N. Brothers. What Happens Without Nickel? Cyclization Reactions of Ethylene with Ethanedithial and Related Molecules. Journal of Computational Chemistry 2018, 39
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- Andrew Mahler, Benjamin G. Janesko, Salvador Moncho, Edward N. Brothers. Why are GGAs so accurate for reaction kinetics on surfaces? Systematic comparison of hybrid vs. nonhybrid DFT for representative reactions. The Journal of Chemical Physics 2017, 146