Reversible Modulation of the Electronic and Spatial Environment around Ni(0) Centers Bearing Multifunctional Carbene Ligands with Triarylaluminum

Yamauchi, Yasuhiro; Mondori, Yutaka; Uetake, Yuta; Takeichi, Yasuo; Kawakita, Takahiro; Sakurai, Hidehiro; Ogoshi, Sensuke; Hoshimoto, Yoichi

doi:https://doi.org/10.1021/jacs.3c06267

Reversible Modulation of the Electronic and Spatial Environment around Ni(0) Centers Bearing Multifunctional Carbene Ligands with Triarylaluminum

Yamauchi, Yasuhiro; Mondori, Yutaka; Uetake, Yuta et al.

Journal of the American Chemical Society, 2023, 145(30), 16938-16947

アクセス数:1,031件（2025-07-26 22:19 集計）

固定URL: https://hdl.handle.net/11094/92546

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タイトル	Reversible Modulation of the Electronic and Spatial Environment around Ni(0) Centers Bearing Multifunctional Carbene Ligands with Triarylaluminum
著者	著者名 Yamauchi, Yasuhiro
	著者名 Mondori, Yutaka
	著者名 Uetake, Yuta
	NRID 1000040636461 1000040636461 researchmap permalink yasuotake1 yasuotake1 著者名 Takeichi, Yasuo
	著者名 Kawakita, Takahiro
	NRID 1000000262147 1000000262147 ORCID 0000-0001-5783-4151 0000-0001-5783-4151 researchmap permalink read0184917 read0184917 Scopus Author ID 7402869823 7402869823 著者名 Sakurai, Hidehiro
	NRID 1000030252589 1000030252589 researchmap permalink read0042792 read0042792 Scopus Author ID 7005303403 7005303403 著者名 Ogoshi, Sensuke
	NRID 1000030710074 1000030710074 ORCID 0000-0003-0882-6109 0000-0003-0882-6109 researchmap permalink YHoshimoto YHoshimoto Scopus Author ID 36463455400 36463455400 著者名 Hoshimoto, Yoichi
キーワード等	Ligands
	Mathematical methods
	Metals
	Molecular structure
	Multifunctional
内容	Yamauchi Y., Mondori Y., Uetake Y., et al. Reversible Modulation of the Electronic and Spatial Environment around Ni(0) Centers Bearing Multifunctional Carbene Ligands with Triarylaluminum. Journal of the American Chemical Society 145, 16938 (2023); https://doi.org/10.1021/jacs.3c06267.
抄録	Designing and modulating the electronic and spatial environments surrounding metal centers is a crucial issue in a wide range of chemistry fields that use organometallic compounds. Herein, we demonstrate a Lewis-acid-mediated reversible expansion, contraction, and transformation of the spatial environment surrounding nickel(0) centers that bear N-phosphine oxide-substituted N-heterocyclic carbenes (henceforth referred to as (S)PoxIms). Reaction between tetrahedral (syn-κ-C,O-(S)PoxIm)Ni(CO)2 and Al(C6F5)3 smoothly afforded heterobimetallic Ni/Al species such as trigonal-planar {κ-C-Ni(CO)2}(μ-anti-(S)PoxIm){κ-O-Al(C6F5)3} via a complexation-induced rotation of the N-phosphine oxide moieties, while the addition of 4-dimethylaminopyridine resulted in the quantitative regeneration of the former Ni complexes. The corresponding interconversion also occurred between (SPoxIm)Ni(η2:η2-diphenyldivinylsilane) and {κ-C-Ni(η2:η2-diene)}(μ-anti-SPoxIm){κ-O-Al(C6F5)3} via the coordination and dissociation of Al(C6F5)3. The shape and size of the space around the Ni(0) center was drastically changed through this Lewis-acid-mediated interconversion. Moreover, the multinuclear NMR, IR, and XAS analyses of the aforementioned carbonyl complexes clarified the details of the changes in the electronic states on the Ni centers; i.e., the electron delocalization was effectively enhanced among the Ni atom and CO ligands in the heterobimetallic Ni/Al species. The results presented in this work thus provide a strategy for reversibly modulating both the electronic and spatial environment of organometallic complexes, in addition to the well-accepted Lewis-base-mediated ligand-substitution methods.
出版者	American Chemical Society
収録物名	Journal of the American Chemical Society
巻(号)	145(30)
ページ	16938-16947
刊行年月	2023-07-19
言語	英語
ハンドルURL	https://hdl.handle.net/11094/92546
PISSN	00027863
eISSN	15205126
NCID	AA12097173
関連情報 (isIdenticalTo)	DOI (出版社版) https://doi.org/10.1021/jacs.3c06267
アクセス権	open access
権利情報	© 2023 The Authors. Published by American Chemical Society.
権利情報	This article is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.
出版タイプ	Version of Record
カテゴリ	学術雑誌論文 Journal Article

資源タイプ	学術雑誌論文
ローカル資源タイプ	学術雑誌論文
DCMI資源タイプ	text
DCTERMS.bibliographicCitation	Journal of the American Chemical Society. 2023, 145(30), p. 16938-16947
DC.title	Reversible Modulation of the Electronic and Spatial Environment around Ni(0) Centers Bearing Multifunctional Carbene Ligands with Triarylaluminum
DC.creator	Yamauchi, Yasuhiro
	Mondori, Yutaka
	Uetake, Yuta
	Takeichi, Yasuo
	Kawakita, Takahiro
	Sakurai, Hidehiro
	Ogoshi, Sensuke
	Hoshimoto, Yoichi
DC.publisher	American Chemical Society
DC.language' scheme='DCTERMS.RFC1766	英語
DC.type' scheme='DCTERMS.DCMIType	text
DCTERMS.issued' scheme='DCTERMS.W3CDTF	2023-07-19
DC.identifier	https://doi.org/10.1021/jacs.3c06267
DC.subject	Ligands
	Mathematical methods
	Metals
	Molecular structure
	Multifunctional
DC.description	Yamauchi Y., Mondori Y., Uetake Y., et al. Reversible Modulation of the Electronic and Spatial Environment around Ni(0) Centers Bearing Multifunctional Carbene Ligands with Triarylaluminum. Journal of the American Chemical Society 145, 16938 (2023); https://doi.org/10.1021/jacs.3c06267.
DCTERMS.abstract	Designing and modulating the electronic and spatial environments surrounding metal centers is a crucial issue in a wide range of chemistry fields that use organometallic compounds. Herein, we demonstrate a Lewis-acid-mediated reversible expansion, contraction, and transformation of the spatial environment surrounding nickel(0) centers that bear N-phosphine oxide-substituted N-heterocyclic carbenes (henceforth referred to as (S)PoxIms). Reaction between tetrahedral (syn-κ-C,O-(S)PoxIm)Ni(CO)2 and Al(C6F5)3 smoothly afforded heterobimetallic Ni/Al species such as trigonal-planar {κ-C-Ni(CO)2}(μ-anti-(S)PoxIm){κ-O-Al(C6F5)3} via a complexation-induced rotation of the N-phosphine oxide moieties, while the addition of 4-dimethylaminopyridine resulted in the quantitative regeneration of the former Ni complexes. The corresponding interconversion also occurred between (SPoxIm)Ni(η2:η2-diphenyldivinylsilane) and {κ-C-Ni(η2:η2-diene)}(μ-anti-SPoxIm){κ-O-Al(C6F5)3} via the coordination and dissociation of Al(C6F5)3. The shape and size of the space around the Ni(0) center was drastically changed through this Lewis-acid-mediated interconversion. Moreover, the multinuclear NMR, IR, and XAS analyses of the aforementioned carbonyl complexes clarified the details of the changes in the electronic states on the Ni centers; i.e., the electron delocalization was effectively enhanced among the Ni atom and CO ligands in the heterobimetallic Ni/Al species. The results presented in this work thus provide a strategy for reversibly modulating both the electronic and spatial environment of organometallic complexes, in addition to the well-accepted Lewis-base-mediated ligand-substitution methods.
DC.rights	© 2023 The Authors. Published by American Chemical Society.
DC.rights	This article is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.
DC.format	92546
citation_title	Reversible Modulation of the Electronic and Spatial Environment around Ni(0) Centers Bearing Multifunctional Carbene Ligands with Triarylaluminum
citation_author	Yamauchi, Yasuhiro
	Mondori, Yutaka
	Uetake, Yuta
	Takeichi, Yasuo
	Kawakita, Takahiro
	Sakurai, Hidehiro
	Ogoshi, Sensuke
	Hoshimoto, Yoichi
citation_publisher	American Chemical Society
citation_language	英語
citation_date	2023-07-19
citation_journal_title	Journal of the American Chemical Society
citation_volume	145
citation_issue	30
citation_firstpage	16938
citation_lastpage	16947
citation_doi	https://doi.org/10.1021/jacs.3c06267
citation_public_url	https://hdl.handle.net/11094/92546

Reversible Modulation of the Electronic and Spatial Environment around Ni(0) Centers Bearing Multifunctional Carbene Ligands with Triarylaluminum

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