Dataset Information

Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe3 Mn-Iodosobenzene Adducts.

ABSTRACT: We report the synthesis, characterization, and reactivity of [LFe3 (PhPz)3 OMn(s PhIO)][OTf]x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene-metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, 57 Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (FeIII2 FeII MnII vs. FeIII3 MnII ) influence oxygen atom transfer in tetranuclear Fe3 Mn clusters. In particular, a one-electron redox change at a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude.

SUBMITTER: de Ruiter G

PROVIDER: S-EPMC5505263 | biostudies-literature | 2017 Apr

REPOSITORIES: biostudies-literature

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Publications

Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe3 Mn-Iodosobenzene Adducts.

de Ruiter Graham G Carsch Kurtis M KM Gul Sheraz S Chatterjee Ruchira R Thompson Niklas B NB Takase Michael K MK Yano Junko J Agapie Theodor T

Angewandte Chemie (International ed. in English) 20170324 17

We report the synthesis, characterization, and reactivity of [LFe3 (PhPz)3 OMn(s PhIO)][OTf]x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene-metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, 57 Fe Mössbauer and X-ray absorption spectroscopy provided ...[more]

PMID: 28338266

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Project description:We report the syntheses, crystal structures, and characterization of the novel cis-dioxomolybdenum(VI) complexes [Tpm*MoVIO2Cl](MoO2Cl3) (1) and [Tpm*MoVIO2Cl](ClO4) (2), which are supported by the charge-neutral tris(3,5-dimethyl-1-pyrazolyl)methane (Tpm*) ligand. A comparison between isostructural [Tpm*MoVIO2Cl]+ and Tp*MoVIO2Cl [Tp* = hydrotris(3,5-dimethyl-1-pyrazolyl)borate] reveals the effects of one unit of overall charge difference on their spectroscopic and electrochemical properties, geometric and electronic structures, and O-atom-transfer (OAT) reactivities, providing new insight into pyranopterin molybdoenzyme OAT reactivity. Computational studies of these molecules indicate that the delocalized positive charge lowers the lowest unoccupied molecular orbital (LUMO) energy of cationic [Tpm*MoO2Cl]+ relative to Tp*MoO2Cl. Despite their virtually identical geometric structures revealed by crystal structures, the MoVI/MoV redox potential of 2 is increased by 350 mV relative to that of Tp*MoVIO2Cl. This LUMO stabilization also contributes to an increased effective electrophilicity of [Tpm*MoO2Cl]+ relative to that of Tp*MoO2Cl, resulting in a more favorable resonant interaction between the molydenum complex LUMO and the highest occupied molecular orbital (HOMO) of the PPh3 substrate. This leads to a greater thermodynamic driving force, an earlier transition state, and a lowered activation barrier for the orbitally controlled first step of the OAT reaction in the Tpm* system relative to the Tp* system. An Eyring plot analysis shows that this initial step yields an O≡MoIV-OPPh3 intermediate via an associative transition state, and the reaction is ∼500-fold faster for 2 than for Tp*MoO2Cl. The second step of the OAT reaction entails solvolysis of the O≡MoIV-OPPh3 intermediate to afford the solvent-substituted MoIV product and is 750-fold faster for the Tpm* system at -15 °C compared to the Tp* system. The observed rate enhancement for the second step is ascribed to a switch of the reaction mechanism from a dissociative pathway for the Tp* system to an alternative associative pathway for the Tpm* system. This is due to a more Lewis acidic MoIV center in the Tpm* system.

Project description:The global oxidation capacity, defined as the tropospheric mean concentration of the hydroxyl radical (OH), controls the lifetime of reactive trace gases in the atmosphere such as methane and carbon monoxide (CO). Models tend to underestimate the methane lifetime and CO concentrations throughout the troposphere, which is consistent with excessive OH. Approximately half of the oxidation of methane and non-methane volatile organic compounds (VOCs) is thought to occur over the oceans where oxidant chemistry has received little validation due to a lack of observational constraints. We use observations from the first two deployments of the NASA ATom aircraft campaign during July-August 2016 and January-February 2017 to evaluate the oxidation capacity over the remote oceans and its representation by the GEOS-Chem chemical transport model. The model successfully simulates the magnitude and vertical profile of remote OH within the measurement uncertainties. Comparisons against the drivers of OH production (water vapor, ozone, and NO y concentrations, ozone photolysis frequencies) also show minimal bias, with the exception of wintertime NO y . The severe model overestimate of NO y during this period may indicate insufficient wet scavenging and/or missing loss on sea-salt aerosols. Large uncertainties in these processes require further study to improve simulated NO y partitioning and removal in the troposphere, but preliminary tests suggest that their overall impact could marginally reduce the model bias in tropospheric OH. During the ATom-1 deployment, OH reactivity (OHR) below 3 km is significantly enhanced, and this is not captured by the sum of its measured components (cOHRobs) or by the model (cOHRmod). This enhancement could suggest missing reactive VOCs but cannot be explained by a comprehensive simulation of both biotic and abiotic ocean sources of VOCs. Additional sources of VOC reactivity in this region are difficult to reconcile with the full suite of ATom measurement constraints. The model generally reproduces the magnitude and seasonality of cOHRobs but underestimates the contribution of oxygenated VOCs, mainly acetaldehyde, which is severely underestimated throughout the troposphere despite its calculated lifetime of less than a day. Missing model acetaldehyde in previous studies was attributed to measurement uncertainties that have been largely resolved. Observations of peroxyacetic acid (PAA) provide new support for remote levels of acetaldehyde. The underestimate in both model acetaldehyde and PAA is present throughout the year in both hemispheres and peaks during Northern Hemisphere summer. The addition of ocean sources of VOCs in the model increases cOHRmod by 3% to 9% and improves model-measurement agreement for acetaldehyde, particularly in winter, but cannot resolve the model summertime bias. Doing so would require 100 Tg yr-1 of a long-lived unknown precursor throughout the year with significant additional emissions in the Northern Hemisphere summer. Improving the model bias for remote acetaldehyde and PAA is unlikely to fully resolve previously reported model global biases in OH and methane lifetime, suggesting that future work should examine the sources and sinks of OH over land.

Dataset Information

Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe3 Mn-Iodosobenzene Adducts.

Publications

Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe<sub>3</sub> Mn-Iodosobenzene Adducts.

Similar Datasets

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