Abstract
Nickel bis(dithiolene) reversibly binds olefins via a known interligand binding mechanism, but the complex has limited practical use, due to a competitive intraligand addition which results in decomposition. The present work examines an alternative nickel-based complex that eliminates the decomposition route. Specifically, we have examined the olefin binding processes of nickel bis(diselenolene) complexes using modern density functional theory. Both the inter- and intraligand adducts of the nickel bis(diselenolenes) are thermodynamically more stable than their dithiolene analogues. We have predicted that nickel bis(diselenolene) complexes do not decompose after the intraligand addition, and that the overall activation energies for the kinetically accessible products are quite small. In short, our computational work predicts that nickel bis(diselenolene) complexes are better electrocatalysts for olefin purification than the previous candidates, superior to the previously studied nickel bis(dithiolene) complexes.
| Original language | English |
|---|---|
| Pages (from-to) | 10182-10191 |
| Number of pages | 10 |
| Journal | Inorganic Chemistry |
| Volume | 55 |
| Issue number | 20 |
| DOIs | |
| Publication status | Published - 17 Oct 2016 |
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ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry
Cite this
Nickel Bis(diselenolene) as a Catalyst for Olefin Purification. / Raju, Rajesh K.; Sredojevic, Dusan N.; Moncho Escriva, Salvador; Brothers, Edward.
In: Inorganic Chemistry, Vol. 55, No. 20, 17.10.2016, p. 10182-10191.Research output: Contribution to journal › Article
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TY - JOUR
T1 - Nickel Bis(diselenolene) as a Catalyst for Olefin Purification
AU - Raju, Rajesh K.
AU - Sredojevic, Dusan N.
AU - Moncho Escriva, Salvador
AU - Brothers, Edward
PY - 2016/10/17
Y1 - 2016/10/17
N2 - Nickel bis(dithiolene) reversibly binds olefins via a known interligand binding mechanism, but the complex has limited practical use, due to a competitive intraligand addition which results in decomposition. The present work examines an alternative nickel-based complex that eliminates the decomposition route. Specifically, we have examined the olefin binding processes of nickel bis(diselenolene) complexes using modern density functional theory. Both the inter- and intraligand adducts of the nickel bis(diselenolenes) are thermodynamically more stable than their dithiolene analogues. We have predicted that nickel bis(diselenolene) complexes do not decompose after the intraligand addition, and that the overall activation energies for the kinetically accessible products are quite small. In short, our computational work predicts that nickel bis(diselenolene) complexes are better electrocatalysts for olefin purification than the previous candidates, superior to the previously studied nickel bis(dithiolene) complexes.
AB - Nickel bis(dithiolene) reversibly binds olefins via a known interligand binding mechanism, but the complex has limited practical use, due to a competitive intraligand addition which results in decomposition. The present work examines an alternative nickel-based complex that eliminates the decomposition route. Specifically, we have examined the olefin binding processes of nickel bis(diselenolene) complexes using modern density functional theory. Both the inter- and intraligand adducts of the nickel bis(diselenolenes) are thermodynamically more stable than their dithiolene analogues. We have predicted that nickel bis(diselenolene) complexes do not decompose after the intraligand addition, and that the overall activation energies for the kinetically accessible products are quite small. In short, our computational work predicts that nickel bis(diselenolene) complexes are better electrocatalysts for olefin purification than the previous candidates, superior to the previously studied nickel bis(dithiolene) complexes.
UR - http://www.scopus.com/inward/record.url?scp=84991768841&partnerID=8YFLogxK
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U2 - 10.1021/acs.inorgchem.6b01295
DO - 10.1021/acs.inorgchem.6b01295
M3 - Article
VL - 55
SP - 10182
EP - 10191
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 20
ER -