Exceptionally Short Tetracoordinated Carbon-Halogen Bonds in Hexafluorodihalocubanes

Sugiyama, Masafumi; Uetake, Yuta; Miyagi, Nozomu; Yoshida, Masaaki; Nozaki, Kyoko; Okazoe, Takashi; Akiyama, Midori

doi:https://doi.org/10.1021/jacs.4c12732

Exceptionally Short Tetracoordinated Carbon-Halogen Bonds in Hexafluorodihalocubanes

Sugiyama, Masafumi; Uetake, Yuta; Miyagi, Nozomu et al.

Journal of the American Chemical Society, 2024, 146(44), 30686-30697

Number of Access:549（2025-07-31 17:05 Counts）

Identifier to cite or link to this item: https://hdl.handle.net/11094/98574

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Title	Exceptionally Short Tetracoordinated Carbon-Halogen Bonds in Hexafluorodihalocubanes
Creator	NRID 1000051002927 1000051002927 CreatorName Sugiyama, Masafumi
	NRID 1000010755440 1000010755440 ORCID 0000-0002-4742-8085 0000-0002-4742-8085 researchmap permalink yutauetake yutauetake Scopus Author ID 56417952700 56417952700 CreatorName Uetake, Yuta
	CreatorName Miyagi, Nozomu
	NRID 1000000582206 1000000582206 CreatorName Yoshida, Masaaki
	NRID 1000060222197 1000060222197 CreatorName Nozaki, Kyoko
	CreatorName Okazoe, Takashi
	NRID 1000050807055 1000050807055 CreatorName Akiyama, Midori
Description	Sugiyama M., Uetake Y., Miyagi N., et al. Exceptionally Short Tetracoordinated Carbon-Halogen Bonds in Hexafluorodihalocubanes. Journal of the American Chemical Society 146, 30686 (2024); https://doi.org/10.1021/jacs.4c12732.
Abstract	Molecules that contain bonds whose length significantly deviates from the average are of interest in the context of understanding the nature and limits of the chemical bonds. However, it is difficult to disentangle the individual contributions of the multiple factors that give rise to such bond-length deviations as reports on such molecules remain scarce. In the present study, we have succeeded in synthesizing hexafluorodihalocubanes of the type C8F6X2 (2) (X = Cl (2Cl), Br (2Br), I (2I)), which represent a new series of molecules with unusual C(sp3)-halogen bonds. The C(sp3)-halogen bonds of 2Cl, 2Br, and 2I, determined via single-crystal X-ray diffraction analysis, are approximately 0.07-0.09 Å shorter than typical C(sp3)-halogen bonds. In particular, the carbon-iodine bonds of 2I are the shortest C(sp3)-I bonds reported to date. The solution-state structures and electronic states of the C(sp3)-halogen bonds in these hexafluorodihalocubanes were analyzed by X-ray absorption spectroscopy, which revealed detailed information on the length of these C(sp3)-halogen bonds in solution and the solid state as well as on the electron-deficient nature of 2. Detailed theoretical calculations and a comparison with halotrinitromethanes (1), which represent another series of molecules with shortened C(sp3)-halogen bonds, revealed that the factors responsible for the shortening of the C(sp3)-halogen bond vary among the different C(sp3)-halogen bonds, i.e., for C(sp3)-Cl and C(sp3)-Br, the s-character and hyperconjugation effects predominate, whereas for C(sp3)-I, the interatomic Coulombic interaction effect prevails.
Publisher	American Chemical Society
Source Title	Journal of the American Chemical Society
Volume (Issue)	146(44)
Page	30686-30697
Date of Issued	2024-11-06
Language	English
Handle URL	https://hdl.handle.net/11094/98574
PISSN	00027863
eISSN	15205126
Relation.isVersionOf	DOI (Publisher Version) https://doi.org/10.1021/jacs.4c12732
Access Rights	embargoed access
CopyRight	This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/jacs.4c12732.
CopyRight	The full-text file will be made open to the public on 6 November 2025 in accordance with the publisher's policy.
oaire:version	Accepted Manuscript
Category	学術雑誌論文 Journal Article

Resource Type	journal article
Local Type	Journal Article
DCTERMS.bibliographicCitation	Journal of the American Chemical Society. 2024, 146(44), p. 30686-30697
DC.title	Exceptionally Short Tetracoordinated Carbon-Halogen Bonds in Hexafluorodihalocubanes
DC.creator	Sugiyama, Masafumi
	Uetake, Yuta
	Miyagi, Nozomu
	Yoshida, Masaaki
	Nozaki, Kyoko
	Okazoe, Takashi
	Akiyama, Midori
DC.publisher	American Chemical Society
DC.language' scheme='DCTERMS.RFC1766	English
DCTERMS.issued' scheme='DCTERMS.W3CDTF	2024-11-06
DC.identifier	https://doi.org/10.1021/jacs.4c12732
DC.description	Sugiyama M., Uetake Y., Miyagi N., et al. Exceptionally Short Tetracoordinated Carbon-Halogen Bonds in Hexafluorodihalocubanes. Journal of the American Chemical Society 146, 30686 (2024); https://doi.org/10.1021/jacs.4c12732.
DCTERMS.abstract	Molecules that contain bonds whose length significantly deviates from the average are of interest in the context of understanding the nature and limits of the chemical bonds. However, it is difficult to disentangle the individual contributions of the multiple factors that give rise to such bond-length deviations as reports on such molecules remain scarce. In the present study, we have succeeded in synthesizing hexafluorodihalocubanes of the type C8F6X2 (2) (X = Cl (2Cl), Br (2Br), I (2I)), which represent a new series of molecules with unusual C(sp3)-halogen bonds. The C(sp3)-halogen bonds of 2Cl, 2Br, and 2I, determined via single-crystal X-ray diffraction analysis, are approximately 0.07-0.09 Å shorter than typical C(sp3)-halogen bonds. In particular, the carbon-iodine bonds of 2I are the shortest C(sp3)-I bonds reported to date. The solution-state structures and electronic states of the C(sp3)-halogen bonds in these hexafluorodihalocubanes were analyzed by X-ray absorption spectroscopy, which revealed detailed information on the length of these C(sp3)-halogen bonds in solution and the solid state as well as on the electron-deficient nature of 2. Detailed theoretical calculations and a comparison with halotrinitromethanes (1), which represent another series of molecules with shortened C(sp3)-halogen bonds, revealed that the factors responsible for the shortening of the C(sp3)-halogen bond vary among the different C(sp3)-halogen bonds, i.e., for C(sp3)-Cl and C(sp3)-Br, the s-character and hyperconjugation effects predominate, whereas for C(sp3)-I, the interatomic Coulombic interaction effect prevails.
DC.rights	This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/jacs.4c12732.
DC.rights	The full-text file will be made open to the public on 6 November 2025 in accordance with the publisher's policy.
DC.format	98574
citation_title	Exceptionally Short Tetracoordinated Carbon-Halogen Bonds in Hexafluorodihalocubanes
citation_author	Sugiyama, Masafumi
	Uetake, Yuta
	Miyagi, Nozomu
	Yoshida, Masaaki
	Nozaki, Kyoko
	Okazoe, Takashi
	Akiyama, Midori
citation_publisher	American Chemical Society
citation_language	English
citation_date	2024-11-06
citation_journal_title	Journal of the American Chemical Society
citation_volume	146
citation_issue	44
citation_firstpage	30686
citation_lastpage	30697
citation_doi	https://doi.org/10.1021/jacs.4c12732
citation_public_url	https://hdl.handle.net/11094/98574

Exceptionally Short Tetracoordinated Carbon-Halogen Bonds in Hexafluorodihalocubanes

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