Jahn-Teller Switching of a Redox-Active Nickel(III) Center in a Homoleptic Thiolato Metalloligand Environment

Kouno, Masahiro; Kuwamura, Naoto; Yoshinari, Nobuto; Kojima, Tatsuhiro; Halcrow, Malcolm A.; Yamagami, Kohei; Sekiyama, Akira; Konno, Takumi

doi:https://doi.org/10.1021/acs.inorgchem.3c00554

Jahn-Teller Switching of a Redox-Active Nickel(III) Center in a Homoleptic Thiolato Metalloligand Environment

Kouno, Masahiro; Kuwamura, Naoto; Yoshinari, Nobuto et al.

Inorganic Chemistry, 2023, 62(24), 9463-9470

Number of Access:750（2025-08-20 22:56 Counts）

Identifier to cite or link to this item: https://hdl.handle.net/11094/92446

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Title	Jahn-Teller Switching of a Redox-Active Nickel(III) Center in a Homoleptic Thiolato Metalloligand Environment
Creator	CreatorName Kouno, Masahiro
	NRID 1000080643791 1000080643791 CreatorName Kuwamura, Naoto
	NRID 1000010583338 1000010583338 ORCID 0000-0003-2457-0967 0000-0003-2457-0967 researchmap permalink read0151149 read0151149 Scopus Author ID 14009212400 14009212400 CreatorName Yoshinari, Nobuto
	NRID 1000080766501 1000080766501 CreatorName Kojima, Tatsuhiro
	CreatorName Halcrow, Malcolm A.
	NRID 1000050823829 1000050823829 CreatorName Yamagami, Kohei
	NRID 1000040294160 1000040294160 researchmap permalink read0051670 read0051670 Scopus Author ID 56266437400 56266437400 CreatorName Sekiyama, Akira
	Scopus Author ID 7202325347 7202325347 NRID 1000050201497 1000050201497 researchmap permalink takumikonno takumikonno CreatorName Konno, Takumi
Subject	Crystal structure
	Nickel
	Solution chemistry
	Transition metals
	X-rays
Description	Kouno M., Kuwamura N., Yoshinari N., et al. Jahn-Teller Switching of a Redox-Active Nickel(III) Center in a Homoleptic Thiolato Metalloligand Environment. Inorganic Chemistry 62, 9463-9470, 19 June 2023, © 2023 American Chemical Society. DOI: 10.1021/acs.inorgchem.3c00554.
Abstract	Treatment of nickel(II) nitrate with the iridium(III) metalloligand fac-[Ir(apt)3] (apt = 3-aminopropanethiolate) gave the trinuclear complex [Ni{Ir(apt)3}2](NO3)3 ([1Ir](NO3)3), in which the nickel center has a formal oxidation state of +III. Chemical or electrochemical oxidation and reduction of [1Ir](NO3)3 generated the corresponding trinuclear complexes [Ni{Ir(apt)3}2](NO3)4 ([1Ir](NO3)4) and [Ni{Ir(apt)3}2](NO3)2 ([1Ir](NO3)2) with one-electron oxidated and reduced states, respectively. Single-crystal X-ray crystallography revealed that the nickel center in [1Ir](NO3)3 is situated in a highly distorted octahedron due to Jahn-Teller effect, while the nickel center in each of [1Ir](NO3)4 and [1Ir](NO3)2 adopts a normal octahedral geometry. Crystals of [1Ir](NO3)3·2H2O are dehydrated on heating while retaining their single-crystallinity. The dehydration induces temperature-dependent dynamic disorder of the Jahn-Teller distortion at the nickel(III) center, which is largely quenched upon rehydration of the crystal.
Publisher	American Chemical Society
Source Title	Inorganic Chemistry
Volume (Issue)	62(24)
Page	9463-9470
Date of Issued	2023-06-19
Language	English
Handle URL	https://hdl.handle.net/11094/92446
PISSN	00201669
eISSN	1520510X
NCID	AA12097184
Relation.isVersionOf	DOI (Publisher Version) https://doi.org/10.1021/acs.inorgchem.3c00554
Access Rights	open access
CopyRight	This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in Inorganic Chemistry, copyright © American Chemical Society after peer review. To access the final edited and published work see https://doi.org/10.1021/acs.inorgchem.3c00554.
oaire:version	Accepted Manuscript
Category	学術雑誌論文 Journal Article

Resource Type	journal article
Local Type	Journal Article
DCMI Type	Text
DCTERMS.bibliographicCitation	Inorganic Chemistry. 2023, 62(24), p. 9463-9470
DC.title	Jahn-Teller Switching of a Redox-Active Nickel(III) Center in a Homoleptic Thiolato Metalloligand Environment
DC.creator	Kouno, Masahiro
	Kuwamura, Naoto
	Yoshinari, Nobuto
	Kojima, Tatsuhiro
	Halcrow, Malcolm A.
	Yamagami, Kohei
	Sekiyama, Akira
	Konno, Takumi
DC.publisher	American Chemical Society
DC.language' scheme='DCTERMS.RFC1766	English
DC.type' scheme='DCTERMS.DCMIType	Text
DCTERMS.issued' scheme='DCTERMS.W3CDTF	2023-06-19
DC.identifier	https://doi.org/10.1021/acs.inorgchem.3c00554
DC.subject	Crystal structure
	Nickel
	Solution chemistry
	Transition metals
	X-rays
DC.description	Kouno M., Kuwamura N., Yoshinari N., et al. Jahn-Teller Switching of a Redox-Active Nickel(III) Center in a Homoleptic Thiolato Metalloligand Environment. Inorganic Chemistry 62, 9463-9470, 19 June 2023, © 2023 American Chemical Society. DOI: 10.1021/acs.inorgchem.3c00554.
DCTERMS.abstract	Treatment of nickel(II) nitrate with the iridium(III) metalloligand fac-[Ir(apt)3] (apt = 3-aminopropanethiolate) gave the trinuclear complex [Ni{Ir(apt)3}2](NO3)3 ([1Ir](NO3)3), in which the nickel center has a formal oxidation state of +III. Chemical or electrochemical oxidation and reduction of [1Ir](NO3)3 generated the corresponding trinuclear complexes [Ni{Ir(apt)3}2](NO3)4 ([1Ir](NO3)4) and [Ni{Ir(apt)3}2](NO3)2 ([1Ir](NO3)2) with one-electron oxidated and reduced states, respectively. Single-crystal X-ray crystallography revealed that the nickel center in [1Ir](NO3)3 is situated in a highly distorted octahedron due to Jahn-Teller effect, while the nickel center in each of [1Ir](NO3)4 and [1Ir](NO3)2 adopts a normal octahedral geometry. Crystals of [1Ir](NO3)3·2H2O are dehydrated on heating while retaining their single-crystallinity. The dehydration induces temperature-dependent dynamic disorder of the Jahn-Teller distortion at the nickel(III) center, which is largely quenched upon rehydration of the crystal.
DC.rights	This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in Inorganic Chemistry, copyright © American Chemical Society after peer review. To access the final edited and published work see https://doi.org/10.1021/acs.inorgchem.3c00554.
DC.format	92446
citation_title	Jahn-Teller Switching of a Redox-Active Nickel(III) Center in a Homoleptic Thiolato Metalloligand Environment
citation_author	Kouno, Masahiro
	Kuwamura, Naoto
	Yoshinari, Nobuto
	Kojima, Tatsuhiro
	Halcrow, Malcolm A.
	Yamagami, Kohei
	Sekiyama, Akira
	Konno, Takumi
citation_publisher	American Chemical Society
citation_language	English
citation_date	2023-06-19
citation_journal_title	Inorganic Chemistry
citation_volume	62
citation_issue	24
citation_firstpage	9463
citation_lastpage	9470
citation_doi	https://doi.org/10.1021/acs.inorgchem.3c00554
citation_public_url	https://hdl.handle.net/11094/92446

Jahn-Teller Switching of a Redox-Active Nickel(III) Center in a Homoleptic Thiolato Metalloligand Environment

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