Constrained phosphine chalcogenide selenoethers supported by peri-substitution

Anna E. Tarcza; Alexandra M. Z. Slawin; Cameron L. Carpenter-Warren; Michael Buehl; Petr Kilian; Brian A. Chalmers

doi:10.3390/molecules28217297

Constrained phosphine chalcogenide selenoethers supported by peri-substitution

Anna E. Tarcza, Alexandra M. Z. Slawin, Cameron L. Carpenter-Warren, Michael Buehl, Petr Kilian, Brian A. Chalmers^*

^*Corresponding author for this work

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

Abstract

A series of phosphorus and selenium peri-substituted acenaphthene species with the phosphino group oxidized by O, S, and Se has been isolated and fully characterized, including by single-crystal X-ray diffraction. The P(V) and Se(II) systems showed fluxional behavior in solution due to the presence of two major rotamers, as evidenced with solution NMR spectroscopy. Using Variable-Temperature NMR (VT NMR) and supported by DFT (Density Functional Theory) calculations and solid-state NMR, the major rotamers in the solid and in solution were identified. All compounds showed a loss of the through-space J_PSe coupling observed in the unoxidized P(III) and Se(II) systems due to the sequestration of the lone pair of the phosphine, which has been previously identified as the major contributor to the coupling pathway.

Original language	English
Article number	7297
Number of pages	18
Journal	Molecules
Volume	28
Issue number	21
DOIs	https://doi.org/10.3390/molecules28217297
Publication status	Published - 27 Oct 2023

Keywords

Peri-substitution
Selenium
Phosphorus
NMR
Single crystal X-ray structures
Rotational conformation
DFT calculations

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10.3390/molecules28217297Licence: CC BY

Tarcza_2023_Molecules_ConstrainedPhosphine_CCBY
Copyright: © 2023 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
Final published version, 1.05 MBLicence: CC BY

Constrained Phosphine Chalcogenide Selenoethers Supported by peri-Substitution dataset (dataset)
Chalmers, B. A. (Creator), Tarcza, A. (Creator), Slawin, A. M. Z. (Contributor), Carpenter-Warren, C. L. (Contributor), Buehl, M. (Contributor) & Kilian, P. (Contributor), University of St Andrews, 9 Nov 2023
DOI: 10.17630/8fe507af-e08a-4ce8-8edb-426149d527e6
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abstract = "A series of phosphorus and selenium peri-substituted acenaphthene species with the phosphino group oxidized by O, S, and Se has been isolated and fully characterized, including by single-crystal X-ray diffraction. The P(V) and Se(II) systems showed fluxional behavior in solution due to the presence of two major rotamers, as evidenced with solution NMR spectroscopy. Using Variable-Temperature NMR (VT NMR) and supported by DFT (Density Functional Theory) calculations and solid-state NMR, the major rotamers in the solid and in solution were identified. All compounds showed a loss of the through-space JPSe coupling observed in the unoxidized P(III) and Se(II) systems due to the sequestration of the lone pair of the phosphine, which has been previously identified as the major contributor to the coupling pathway. ",

keywords = "Peri-substitution, Selenium, Phosphorus, NMR, Single crystal X-ray structures, Rotational conformation, DFT calculations",

author = "Tarcza, {Anna E.} and Slawin, {Alexandra M. Z.} and Carpenter-Warren, {Cameron L.} and Michael Buehl and Petr Kilian and Chalmers, {Brian A.}",

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T1 - Constrained phosphine chalcogenide selenoethers supported by peri-substitution

AU - Tarcza, Anna E.

AU - Slawin, Alexandra M. Z.

AU - Carpenter-Warren, Cameron L.

AU - Buehl, Michael

AU - Kilian, Petr

AU - Chalmers, Brian A.

PY - 2023/10/27

Y1 - 2023/10/27

N2 - A series of phosphorus and selenium peri-substituted acenaphthene species with the phosphino group oxidized by O, S, and Se has been isolated and fully characterized, including by single-crystal X-ray diffraction. The P(V) and Se(II) systems showed fluxional behavior in solution due to the presence of two major rotamers, as evidenced with solution NMR spectroscopy. Using Variable-Temperature NMR (VT NMR) and supported by DFT (Density Functional Theory) calculations and solid-state NMR, the major rotamers in the solid and in solution were identified. All compounds showed a loss of the through-space JPSe coupling observed in the unoxidized P(III) and Se(II) systems due to the sequestration of the lone pair of the phosphine, which has been previously identified as the major contributor to the coupling pathway.

AB - A series of phosphorus and selenium peri-substituted acenaphthene species with the phosphino group oxidized by O, S, and Se has been isolated and fully characterized, including by single-crystal X-ray diffraction. The P(V) and Se(II) systems showed fluxional behavior in solution due to the presence of two major rotamers, as evidenced with solution NMR spectroscopy. Using Variable-Temperature NMR (VT NMR) and supported by DFT (Density Functional Theory) calculations and solid-state NMR, the major rotamers in the solid and in solution were identified. All compounds showed a loss of the through-space JPSe coupling observed in the unoxidized P(III) and Se(II) systems due to the sequestration of the lone pair of the phosphine, which has been previously identified as the major contributor to the coupling pathway.

KW - Peri-substitution

KW - Selenium

KW - Phosphorus

KW - NMR

KW - Single crystal X-ray structures

KW - Rotational conformation

KW - DFT calculations

U2 - 10.3390/molecules28217297

DO - 10.3390/molecules28217297

M3 - Article

SN - 1420-3049

VL - 28

JO - Molecules

JF - Molecules

IS - 21

M1 - 7297

ER -

Constrained phosphine chalcogenide selenoethers supported by peri-substitution

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Datasets

Constrained Phosphine Chalcogenide Selenoethers Supported by peri-Substitution dataset (dataset)

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