jp8b05707_si_001.pdf (2.04 MB)
Reversible Olefin Addition to Extended Lattices of a Nickel–Selenium Framework
journal contribution
posted on 2018-09-13, 00:00 authored by Dušan N. Sredojević, Salvador Moncho, Rajesh Kumar Raju, Milivoj R. Belić, Edward N. BrothersWe
performed density functional theory computations to study the
structural and electronic properties as the basis of ethylene addition
activity for [Ni(XC)4]n (X
= Se, S)-extended lattices. We demonstrated that the mechanism of
ethylene cycloaddition to a periodic [Ni(SeC)4]n two-dimensional (2D) network is analogous to that
previously described for [Ni(SC)4]n 2D sheets and similar to the metal bis(dithiolene) molecular
complexes [M(S2C2R2)2]
(M = Ni, Pd, Pt, Co, Cu). These nanosheet materials avoid decomposition
upon olefin addition, which is one of the main limitations of the
molecular metal bis(dithiolene) complexes, as we find the decomposition
processes to be thermodynamically unfavorable. Our calculations also
suggest that the preferred conformation of the [Ni(SeC)4]n bilayer lattice is parallel displaced,
with the Se atoms positioned above the Ni atoms, which is different
from the eclipsed conformation found for [Ni(SC)4]n. We also managed to optimize an adduct of
[Ni(SC)4]n in the bilayer form,
which exceed the ethylene coverage of molecular complexes. We calculate
that the preferred three-dimensional geometry of the stacked sheets
is eclipsed because of strong van der Waals interactions. Such an
arrangement of the sheets indicates that these materials should be
highly porous, pointing to the high capacity for olefin bindings.
Indeed, a few moderately stable ethylene adducts have been located.
Owing to their unique structures and chemical reactivity, these newly
predicted materials can be potentially developed as electrocatalysts
for olefin purification.
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Keywords
Extended Latticesethylene addition activitychemical reactivitydecomposition processesolefin additionnanosheet materialsn 2 D sheetsethylene coverageethylene cycloadditionolefin purificationReversible Olefin Additionvan der Waals interactionsbilayer formtheory computationsSe atomsn bilayer latticeNi atomscomplexethylene adductsolefin bindings
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