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High-resolution X-ray diffraction determination of the electron density of 1-(8-PhSC10H6)SS(C10H6SPh-8′)-1′ with the QTAIM approach: evidence for S4 σ(4c–6e) at the naphthalene peri-positions

High-resolution X-ray diffraction determination of the electron density of 1-(8-PhSC10H6)SS(C10H6SPh-8′)-1′ with the QTAIM approach: evidence for S4 σ(4c–6e) at the naphthalene peri-positions
High-resolution X-ray diffraction determination of the electron density of 1-(8-PhSC10H6)SS(C10H6SPh-8′)-1′ with the QTAIM approach: evidence for S4 σ(4c–6e) at the naphthalene peri-positions
An extended hypervalent S4 σ(4c–6e) system was confirmed for the linear BS-∗-AS-∗-AS-∗-BS interaction in 1-(8-PhBSC10H6)AS–AS(C10H6BSPh-8′)-1′ (1) via high-resolution X-ray diffraction determination of electron densities. The presence of bond critical points (BCPs; ∗) on the bond paths confirms the nature and extent of this interaction. The recently developed QTAIM dual functional analysis (QTAIM-DFA) approach was also applied to elucidate the nature of the interaction. Total electron energy densities Hb(rc) were plotted versus Hb(rc) − Vb(rc)/2 for the interaction at the BCPs, where Vb(rc) represents the potential energy densities at the BCP. The results indicate that although the data for an interaction in the fully optimized structure corresponds to a static nature, the data obtained for the perturbed structures around it represent the dynamic nature of the interaction in QTAIM-DFA. The former classifies the interaction and the latter characterises it. Although AS-∗-AS in 1 is classified by a shared shell interaction and exhibits weak covalent character, AS-∗-BS is characterized as having typical hydrogen-bond nature with covalent properties in the region of the regular closed shell interactions. The experimental results are supported by matching theoretical calculations throughout, particularly for the extended hypervalent E4 σ(4c–6e) (E = S) interaction.
2046-2069
9651-9660
Tsubomoto, Yutaka
e8b51970-92ea-442c-8b04-88da8b27a9db
Hayashi, Satoko
adcce441-77a6-429f-b03c-83f995187ce8
Nakanishi, Waro
3e3b7668-7de9-406f-b783-97a1bc37dd74
Mapp, Lucy, Kristina
b90136ce-37b0-464a-8934-d44a8c2d7e48
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Tsubomoto, Yutaka
e8b51970-92ea-442c-8b04-88da8b27a9db
Hayashi, Satoko
adcce441-77a6-429f-b03c-83f995187ce8
Nakanishi, Waro
3e3b7668-7de9-406f-b783-97a1bc37dd74
Mapp, Lucy, Kristina
b90136ce-37b0-464a-8934-d44a8c2d7e48
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8

Tsubomoto, Yutaka, Hayashi, Satoko, Nakanishi, Waro, Mapp, Lucy, Kristina and Coles, Simon J. (2018) High-resolution X-ray diffraction determination of the electron density of 1-(8-PhSC10H6)SS(C10H6SPh-8′)-1′ with the QTAIM approach: evidence for S4 σ(4c–6e) at the naphthalene peri-positions. RSC Advances, 2018 (18), 9651-9660. (doi:10.1039/C7RA13636F).

Record type: Article

Abstract

An extended hypervalent S4 σ(4c–6e) system was confirmed for the linear BS-∗-AS-∗-AS-∗-BS interaction in 1-(8-PhBSC10H6)AS–AS(C10H6BSPh-8′)-1′ (1) via high-resolution X-ray diffraction determination of electron densities. The presence of bond critical points (BCPs; ∗) on the bond paths confirms the nature and extent of this interaction. The recently developed QTAIM dual functional analysis (QTAIM-DFA) approach was also applied to elucidate the nature of the interaction. Total electron energy densities Hb(rc) were plotted versus Hb(rc) − Vb(rc)/2 for the interaction at the BCPs, where Vb(rc) represents the potential energy densities at the BCP. The results indicate that although the data for an interaction in the fully optimized structure corresponds to a static nature, the data obtained for the perturbed structures around it represent the dynamic nature of the interaction in QTAIM-DFA. The former classifies the interaction and the latter characterises it. Although AS-∗-AS in 1 is classified by a shared shell interaction and exhibits weak covalent character, AS-∗-BS is characterized as having typical hydrogen-bond nature with covalent properties in the region of the regular closed shell interactions. The experimental results are supported by matching theoretical calculations throughout, particularly for the extended hypervalent E4 σ(4c–6e) (E = S) interaction.

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Accepted/In Press date: 20 February 2018
e-pub ahead of print date: 5 March 2018

Identifiers

Local EPrints ID: 418999
URI: https://eprints.soton.ac.uk/id/eprint/418999
ISSN: 2046-2069
PURE UUID: ed59bb93-d8ee-4323-b1d3-1863dde54460
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

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Date deposited: 27 Mar 2018 16:30
Last modified: 06 Apr 2018 16:30

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Author: Yutaka Tsubomoto
Author: Satoko Hayashi
Author: Waro Nakanishi
Author: Lucy, Kristina Mapp
Author: Simon J. Coles ORCID iD

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