Dataset Information

The Dimethylbismuth Cation: Entry Into Dative Bi-Bi Bonding and Unconventional Methyl Exchange.

ABSTRACT: The isolation of simple, fundamentally important, and highly reactive organometallic compounds remains among the most challenging tasks in synthetic chemistry. The detailed characterization of such compounds is key to the discovery of novel bonding scenarios and reactivity. The dimethylbismuth cation, [BiMe₂ (SbF₆ )] (1), has been isolated and characterized. Its reaction with BiMe₃ gives access to an unprecedented dative bond, a Bi→Bi donor-acceptor interaction. The exchange of methyl groups (arguably the simplest hydrocarbon moiety) between different metal atoms is among the most principal types of reactions in organometallic chemistry. The reaction of 1 with BiMe₃ enables an S_E 2(back)-type methyl exchange, which is, for the first time, investigated in detail for isolable, (pseudo-)homoleptic main-group compounds.

SUBMITTER: Ramler J

PROVIDER: S-EPMC8596701 | biostudies-literature | 2021 Nov

REPOSITORIES: biostudies-literature

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The Dimethylbismuth Cation: Entry Into Dative Bi-Bi Bonding and Unconventional Methyl Exchange.

Ramler Jacqueline J Fantuzzi Felipe F Geist Felix F Hanft Anna A Braunschweig Holger H Engels Bernd B Lichtenberg Crispin C

Angewandte Chemie (International ed. in English) 20210906 46

The isolation of simple, fundamentally important, and highly reactive organometallic compounds remains among the most challenging tasks in synthetic chemistry. The detailed characterization of such compounds is key to the discovery of novel bonding scenarios and reactivity. The dimethylbismuth cation, [BiMe2 (SbF6 )] (1), has been isolated and characterized. Its reaction with BiMe3 gives access to an unprecedented dative bond, a Bi→Bi donor-acceptor interaction. ...[more]

PMID: 34378855

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Project description:The poromechanical properties of unconventional reservoir materials are in large part dictated by their mineralogy. Since these properties govern the response to stress experienced during hydraulic fracturing, fluid production, and fluid injection, they play a central role in the formation of microcracks or bedding delaminations which ultimately dominate mass transport. In this work we study access to the porosity of end member unconventional reservoir materials, where the end members are predominantly dictated by carbonate content. Access to the porosity is quantified using state of the art 3D x-ray computed tomography coupled with physics informed data analytics. Xenon gas, which attenuates x-rays, provides a spatiotemporal map of access to the porosity. The accessible porosity is quantified over a range of net confining stress relevant to the manmade disturbances listed above. These experiments demonstrate that heavily carbonated mudstones are nearly impermeable at the core (~ cm) scale, while carbonate free analogues afford better access to the microstructure. Consistent with previous qualitative 2D radiographs, access to the interior of the clastic mudstones is first observed along planar microcracks, followed by slow penetration into the surrounding matrix. Physics informed data analytics of the 3D tomography measurements presented here show that these microcracks do not permit uniform access to the adjacent rock matrix. In addition, variation of the effective pressure elucidates the mechanisms that govern fracture/matrix fluid exchange. Under conditions consistent with hydrocarbon production fluid accumulates in the immediate vicinity of the nearest microcrack. While there is clear evidence that, as intended, part of this accumulation is from the more distant matrix, fluid is also squeezed out of the microcrack. The fluid build-up at the microcrack indicates that migration out of the rock is hindered by the coupled poroelastic response of the microcrack and adjacent rock matrix. We show that these mechanisms ultimately account for the meager oil recovery factors realized in practice. These insights have implications for making reservoir scale predictions based on core scale observations, and provide a basis for devising new asset development techniques to access more porosity, and enhance fluid extraction. Finally, these findings shed light on key features and mechanisms that govern shale storage capacity, with relevance to other important industrial processes, such as geologic CO2 storage.

Dataset Information

The Dimethylbismuth Cation: Entry Into Dative Bi-Bi Bonding and Unconventional Methyl Exchange.

Publications

The Dimethylbismuth Cation: Entry Into Dative Bi-Bi Bonding and Unconventional Methyl Exchange.

Similar Datasets

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