Complexes of Zinc-Coordinated Heteroaromatic N-Oxides with Pyrene: Lewis Acid Effects on the Multicenter Donor–Acceptor Bonding
Yakov P. Nizhnik, Erin Hansen, Cayden Howard, Matthias Zeller, Sergiy V. Rosokha
TL;DR
This study explores how zinc coordination affects the bonding between N-oxides and pyrene, revealing stronger interactions through electrostatic and orbital effects.
Contribution
The paper introduces new insights into how Lewis acids like ZnCl2 enhance multicenter donor–acceptor bonding in N-oxide–pyrene complexes.
Findings
Coordination with ZnCl2 increases the positive electrostatic potential on π-acceptor surfaces.
ZnCl2 coordination strengthens multicenter bonding through electrostatic and molecular-orbital interactions.
Dark co-crystals form from Zn-coordinated N-oxides and pyrene, similar to protonated or BF3-bonded systems.
Abstract
4-Nitroquinoline-N-oxide (NQO) and 4-nitropyridine-N-oxide (NPO) are important precursors for the synthesis of substituted heterocycles while NQO is a popular model mutagen and carcinogen broadly used in cancer research; intermolecular interactions are critical for their reactions or functioning in vivo. Herein, the effects of the coordination of N-oxide’s oxygen atom to Lewis acids on multicenter donor–acceptor bonding were explored via a combination of experimental and computational studies of the complexes of NQO and NPO with a typical π-electron donor, pyrene. Coordination with ZnCl2 increased the positive electrostatic potentials on the surfaces of these π-acceptors and lowered the energy of their LUMO. Analogous effects were observed upon the protonation of the N-oxides’ oxygen or bonding with boron trifluoride. The interaction of ZnCl2, NPO, or NQO and pyrene resulted in the…
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Taxonomy
TopicsOrganic Chemistry Cycloaddition Reactions · Crystallography and molecular interactions · Chemical Reaction Mechanisms