Kouno, M, Kuwamura, N, Yoshinari, N et al. (5 more authors) (2023) Jahn–Teller Switching of a Redox-Active Nickel(III) Center in a Homoleptic Thiolato Metalloligand Environment. Inorganic Chemistry. ISSN 0020-1669
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.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | Copyright © 2023 American Chemical Society. This is an author produced version of an article published in Inorganic Chemistry. Uploaded in accordance with the publisher's self-archiving policy. |
Dates: |
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Institution: | The University of Leeds |
Academic Units: | The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Chemistry (Leeds) > Inorganic Chemistry (Leeds) |
Depositing User: | Symplectic Publications |
Date Deposited: | 06 Jul 2023 16:19 |
Last Modified: | 06 Jun 2024 00:13 |
Status: | Published online |
Publisher: | American Chemical Society |
Identification Number: | 10.1021/acs.inorgchem.3c00554 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:200069 |