Dataset Information

Oxygen transfer in electrophilic epoxidation probed by 17O NMR: differentiating between oxidants and role of spectator metal oxo.

ABSTRACT: Peroxide compounds are used both in laboratory and industrial processes for the electrophilic epoxidation of olefins. Using NMR-spectroscopy, we investigate why certain peroxides engage in this type of reaction while others require activation by metal catalysts, e.g. methyltrioxorhenium (MTO). More precisely, an analysis of 17O NMR chemical shift and quadrupolar coupling parameters provides insights into the relative energy of specific frontier molecular orbitals relevant for reactivity. For organic peroxides or H2O2 a large deshielding is indicative of an energetically high-lying lone-pair on oxygen in combination with a low-lying ?*(O-O) orbital. This feature is particularly pronounced in species that engage in electrophilic epoxidation, such as peracids or dimethyldioxirane (DMDO), and much less pronounced in unreactive peroxides such as H2O2 and ROOH, which can however be activated by transition-metal catalysts. In fact, for the proposed active peroxo species in MTO-catalyzed electrophilic epoxidation with H2O2 an analysis of the 17O NMR chemical shift highlights specific ?- and ?-type orbital interactions between the so-called metal spectator oxo and the peroxo moieties that raise the energy of the high-lying lone-pair on oxygen, thus increasing the reactivity of the peroxo species.

SUBMITTER: Ehinger C

PROVIDER: S-EPMC6369410 | biostudies-literature | 2019 Feb

REPOSITORIES: biostudies-literature

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Oxygen transfer in electrophilic epoxidation probed by 17O NMR: differentiating between oxidants and role of spectator metal oxo.

Ehinger Christian C Gordon Christopher P CP Copéret Christophe C

Chemical science 20181203 6

Peroxide compounds are used both in laboratory and industrial processes for the electrophilic epoxidation of olefins. Using NMR-spectroscopy, we investigate why certain peroxides engage in this type of reaction while others require activation by metal catalysts, e.g. methyltrioxorhenium (MTO). More precisely, an analysis of 17O NMR chemical shift and quadrupolar coupling parameters provides insights into the relative energy of specific frontier molecular orbitals relevant for r ...[more]

PMID: 30842846

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Project description:The spectroscopic study of oxygen, a vital element in materials, physical, and life sciences, is of tremendous fundamental and practical importance. 17O solid-state NMR (SSNMR) spectroscopy has evolved into an ideal site-specific characterization tool, furnishing valuable information on the local geometric and bonding environments about chemically distinct and, in some favorable cases, crystallographically inequivalent oxygen sites. However, 17O is a challenging nucleus to study via SSNMR, as it suffers from low sensitivity and resolution, owing to the quadrupolar interaction and low 17O natural abundance. Herein, we report a significant advance in 17O SSNMR spectroscopy. 17O isotopic enrichment and the use of an ultrahigh 35.2 T magnetic field have unlocked the identification of many inequivalent carboxylate oxygen sites in the as-made and activated phases of the metal-organic framework (MOF) α-Mg3(HCOO)6. The subtle 17O spectral differences between the as-made and activated phases yield detailed information about host-guest interactions, including insight into nonconventional O···H-C hydrogen bonding. Such weak interactions often play key roles in the applications of MOFs, such as gas adsorption and biomedicine, and are usually difficult to study via other characterization routes. The power of performing 17O SSNMR experiments at an ultrahigh magnetic field of 35.2 T for MOF characterization is further demonstrated by examining activation of the MIL-53(Al) MOF. The sensitivity and resolution enhanced at 35.2 T allows partially and fully activated MIL-53(Al) to be unambiguously distinguished and also permits several oxygen environments in the partially activated phase to be tentatively identified. This demonstration of the very high resolution of 17O SSNMR recorded at the highest magnetic field accessible to chemists to date illustrates how a broad variety of scientists can now study oxygen-containing materials and obtain previously inaccessible fine structural information.

Dataset Information

Oxygen transfer in electrophilic epoxidation probed by 17O NMR: differentiating between oxidants and role of spectator metal oxo.

Publications

Oxygen transfer in electrophilic epoxidation probed by <sup>17</sup>O NMR: differentiating between oxidants and role of spectator metal oxo.

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