Abstract
Although weak intermolecular interactions are the essence of most processes of key importance in medicine, industry, environment, and life cycles, their characterization is still not sufficient. Enzymatic dehalogenations that involve chloride anion interaction within a host–guest framework is one of the many examples. Recently published experimental results on host–guest systems provided us with models suitable to assess isotopic consequences of these noncovalent interactions. Herein, we report the influence of environmental and structural variations on chlorine isotope effects. We show that these effects, although small, may obscure mechanistic interpretations, as well as analytical protocols of dehalogenation processes.
Highlights
IntroductionWeak intermolecular interactions are the essence of many processes of key importance to life (e.g., the formation of Michaelis complexes during enzymatic reactions), industry (e.g., interactions within cavities, perovskites, or metal−organic frameworks (MOFs)), and medicine (e.g., host−guest interactions in drug delivery systems) to name a few most typical examples
Weak intermolecular interactions are the essence of many processes of key importance to life, industry (e.g., interactions within cavities, perovskites, or metal−organic frameworks (MOFs)), and medicine to name a few most typical examples
For the process of transferring the isolated chloride anion from the gas phase to the aqueous solution, where it forms a network of strong hydrogen bonds with the first solvation shell, the corresponding isotope effect calculated at the quantum mechanics/molecular mechanics (QM/MM) level using the model presented in Figure 2b is 0.9956
Summary
Weak intermolecular interactions are the essence of many processes of key importance to life (e.g., the formation of Michaelis complexes during enzymatic reactions), industry (e.g., interactions within cavities, perovskites, or metal−organic frameworks (MOFs)), and medicine (e.g., host−guest interactions in drug delivery systems) to name a few most typical examples. Due to our research involvement in enzymatic and environmentally oriented dehalogenation processes,[1−3] in chlorine isotopic fractionations, as well as the key role of chloride in many lifecontrolling processes,[4] host−guest interactions between the chloride anion as a guest in different host frameworks are of special interest In this respect, several recently published results provide a unique opportunity for their theoretical modeling. The question of how the solvent polarity affects host−guest interactions with chloride being a guest has been addressed in the past.[5−8] Most recently, linear free energy dependence on ET(30) has been demonstrated[9] for the bis(arylethynyl phenylurea) host, 1 Within this framework, chloride interacts with the host via four N−H···Cl hydrogen bonds and with one C−H bond.
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