The Challenging World of Simple Inorganic Rings: Revisiting Roesky's Ketone and Roesky's Sulfoxide

Ana V. Cunha; Remco W.A. Havenith; Christian Van Alsenoy; Frank Blockhuys

doi:10.1002/chem.202302449

The Challenging World of Simple Inorganic Rings: Revisiting Roesky's Ketone and Roesky's Sulfoxide

Ana V. Cunha, Remco W.A. Havenith, Christian Van Alsenoy, Frank Blockhuys

Research output: Contribution to journal › Article › peer-review

Abstract

The surprising differences between the experimental solid-state and calculated gas-phase structures of 5-oxo-1,3,2,4-dithiadiazole (Roesky's ketone, 1) and 1-oxo-1,2,4,3,5-trithiadiazole (Roesky's sulfoxide, 2), identified and studied in a series of papers published between 2004 and 2010 but then never satisfactorily explained, have been revisited, making use of the more advanced computational possibilities currently available. The previous calculations’ considerable overestimations of the C−S and S−S bond lengths in 1 and 2, respectively, have been partly explained based on the results of periodic calculations and the application of Valence Bond (VB) Theory. In the case of 1, the crystal environment appears to stabilize a structure with a highly polarized C=O bond, which features a C−S bond with considerable double-bond character – an effect which does not exist for the isolated molecule – explaining the much shorter bond in the solid state. For 2, a similar conclusion can be drawn for the S−S distance. For both compounds, though, packing effects are not the sole source of the differences: the inability of Density Functional Theory (DFT) to properly deal with the electronic structures of these apparently simple main-group systems remains a contributing factor.

Original language	English
Article number	e202302449
Journal	Chemistry - A European Journal
Volume	29
Issue number	67
DOIs	https://doi.org/10.1002/chem.202302449
State	Published - Dec 1 2023
Externally published	Yes

Funding

This research used resources (Summit) of the Oak Ridge Leadership Computing Facility at the Oak Ridge National Laboratory, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE‐AC05‐00OR22725 (DD). This work was sponsored by NWO Exact and Natural Sciences for the use of supercomputer facilities (EINF‐431 and contract no. 17197 7095). R.W.A.H. and A.V.C. thank S. Dolas (SURF, NL) for allowing us to perform calculations on the experimental AMD platform kleurplaat maintained and operated by SURF Open Innovation Lab. We would like to thank the Center for Information Technology of the University of Groningen for their support and for providing access to the Peregrine/Habrok high performance computing cluster. This research used resources (Summit) of the Oak Ridge Leadership Computing Facility at the Oak Ridge National Laboratory, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC05-00OR22725 (DD). This work was sponsored by NWO Exact and Natural Sciences for the use of supercomputer facilities (EINF-431 and contract no. 17197 7095). R.W.A.H. and A.V.C. thank S. Dolas (SURF, NL) for allowing us to perform calculations on the experimental AMD platform kleurplaat maintained and operated by SURF Open Innovation Lab. We would like to thank the Center for Information Technology of the University of Groningen for their support and for providing access to the Peregrine/Habrok high performance computing cluster.

Keywords

dithiadiazole
molecular geometry
solid-state geometry
trithiadiazole
valence bond theory

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10.1002/chem.202302449

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title = "The Challenging World of Simple Inorganic Rings: Revisiting Roesky's Ketone and Roesky's Sulfoxide",

abstract = "The surprising differences between the experimental solid-state and calculated gas-phase structures of 5-oxo-1,3,2,4-dithiadiazole (Roesky's ketone, 1) and 1-oxo-1,2,4,3,5-trithiadiazole (Roesky's sulfoxide, 2), identified and studied in a series of papers published between 2004 and 2010 but then never satisfactorily explained, have been revisited, making use of the more advanced computational possibilities currently available. The previous calculations{\textquoteright} considerable overestimations of the C−S and S−S bond lengths in 1 and 2, respectively, have been partly explained based on the results of periodic calculations and the application of Valence Bond (VB) Theory. In the case of 1, the crystal environment appears to stabilize a structure with a highly polarized C=O bond, which features a C−S bond with considerable double-bond character – an effect which does not exist for the isolated molecule – explaining the much shorter bond in the solid state. For 2, a similar conclusion can be drawn for the S−S distance. For both compounds, though, packing effects are not the sole source of the differences: the inability of Density Functional Theory (DFT) to properly deal with the electronic structures of these apparently simple main-group systems remains a contributing factor.",

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author = "Cunha, \{Ana V.\} and Havenith, \{Remco W.A.\} and \{Van Alsenoy\}, Christian and Frank Blockhuys",

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AB - The surprising differences between the experimental solid-state and calculated gas-phase structures of 5-oxo-1,3,2,4-dithiadiazole (Roesky's ketone, 1) and 1-oxo-1,2,4,3,5-trithiadiazole (Roesky's sulfoxide, 2), identified and studied in a series of papers published between 2004 and 2010 but then never satisfactorily explained, have been revisited, making use of the more advanced computational possibilities currently available. The previous calculations’ considerable overestimations of the C−S and S−S bond lengths in 1 and 2, respectively, have been partly explained based on the results of periodic calculations and the application of Valence Bond (VB) Theory. In the case of 1, the crystal environment appears to stabilize a structure with a highly polarized C=O bond, which features a C−S bond with considerable double-bond character – an effect which does not exist for the isolated molecule – explaining the much shorter bond in the solid state. For 2, a similar conclusion can be drawn for the S−S distance. For both compounds, though, packing effects are not the sole source of the differences: the inability of Density Functional Theory (DFT) to properly deal with the electronic structures of these apparently simple main-group systems remains a contributing factor.

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The Challenging World of Simple Inorganic Rings: Revisiting Roesky's Ketone and Roesky's Sulfoxide

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