Dennis A Buschmann, H Martin Dietrich, James Durrant, Cäcilia Maichle-Mössmer, Jinkui Tang, Richard A Layfield, Reiner Anwander
{"title":"稀土金属的多金属半夹层配合物。","authors":"Dennis A Buschmann, H Martin Dietrich, James Durrant, Cäcilia Maichle-Mössmer, Jinkui Tang, Richard A Layfield, Reiner Anwander","doi":"10.1021/acs.inorgchem.4c04785","DOIUrl":null,"url":null,"abstract":"<p><p>Multimetallic half-sandwich complexes of the paramagnetic lanthanides gadolinium, terbium, dysprosium, holmium, and erbium as well as of diamagnetic yttrium are readily accessible via AlMe<sub>4</sub>/halogenido exchange reactions of Cp*Ln(AlMe<sub>4</sub>)<sub>2</sub> with the mild halogenido transfer reagents Me<sub>3</sub>SiI and Me<sub>3</sub>GeX (Cp* = C<sub>5</sub>Me<sub>5</sub>; X = Br, Cl). Depending on the rare-earth-metal center and halogenido ion size, complexes with distinct structural motifs and nuclearities are obtained, including dimeric compounds [Cp*Ln(AlMe<sub>4</sub>)(μ<sub>2</sub>-Cl)]<sub>2</sub> for the smaller metal centers Ln = Ho, Er, iodido-bridged tetranuclear rings [Cp*Ln(μ<sub>2</sub>-I)<sub>2</sub>]<sub>4</sub> (Ln = Y, Tb, Dy, Ho, Er), and a heterobimetallic tetramethylaluminato-bridged gadolinium cluster [Cp*<sub>4</sub>Gd<sub>4</sub>I<sub>7</sub>(AlMe<sub>4</sub>)]<sub>2</sub>. The tetranuclear dysprosium complex [Cp*Dy(μ<sub>2</sub>-I)<sub>2</sub>]<sub>4</sub> shows single-molecule magnet (SMM) behavior in zero applied field with an effective energy barrier of 164(10) cm<sup>-1</sup>.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":" ","pages":"2795-2808"},"PeriodicalIF":4.7000,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Multimetallic Half-Sandwich Complexes of the Rare-Earth Metals.\",\"authors\":\"Dennis A Buschmann, H Martin Dietrich, James Durrant, Cäcilia Maichle-Mössmer, Jinkui Tang, Richard A Layfield, Reiner Anwander\",\"doi\":\"10.1021/acs.inorgchem.4c04785\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>Multimetallic half-sandwich complexes of the paramagnetic lanthanides gadolinium, terbium, dysprosium, holmium, and erbium as well as of diamagnetic yttrium are readily accessible via AlMe<sub>4</sub>/halogenido exchange reactions of Cp*Ln(AlMe<sub>4</sub>)<sub>2</sub> with the mild halogenido transfer reagents Me<sub>3</sub>SiI and Me<sub>3</sub>GeX (Cp* = C<sub>5</sub>Me<sub>5</sub>; X = Br, Cl). Depending on the rare-earth-metal center and halogenido ion size, complexes with distinct structural motifs and nuclearities are obtained, including dimeric compounds [Cp*Ln(AlMe<sub>4</sub>)(μ<sub>2</sub>-Cl)]<sub>2</sub> for the smaller metal centers Ln = Ho, Er, iodido-bridged tetranuclear rings [Cp*Ln(μ<sub>2</sub>-I)<sub>2</sub>]<sub>4</sub> (Ln = Y, Tb, Dy, Ho, Er), and a heterobimetallic tetramethylaluminato-bridged gadolinium cluster [Cp*<sub>4</sub>Gd<sub>4</sub>I<sub>7</sub>(AlMe<sub>4</sub>)]<sub>2</sub>. The tetranuclear dysprosium complex [Cp*Dy(μ<sub>2</sub>-I)<sub>2</sub>]<sub>4</sub> shows single-molecule magnet (SMM) behavior in zero applied field with an effective energy barrier of 164(10) cm<sup>-1</sup>.</p>\",\"PeriodicalId\":40,\"journal\":{\"name\":\"Inorganic Chemistry\",\"volume\":\" \",\"pages\":\"2795-2808\"},\"PeriodicalIF\":4.7000,\"publicationDate\":\"2025-02-17\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Inorganic Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.inorgchem.4c04785\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"2025/1/31 0:00:00\",\"PubModel\":\"Epub\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.inorgchem.4c04785","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2025/1/31 0:00:00","PubModel":"Epub","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Multimetallic Half-Sandwich Complexes of the Rare-Earth Metals.
Multimetallic half-sandwich complexes of the paramagnetic lanthanides gadolinium, terbium, dysprosium, holmium, and erbium as well as of diamagnetic yttrium are readily accessible via AlMe4/halogenido exchange reactions of Cp*Ln(AlMe4)2 with the mild halogenido transfer reagents Me3SiI and Me3GeX (Cp* = C5Me5; X = Br, Cl). Depending on the rare-earth-metal center and halogenido ion size, complexes with distinct structural motifs and nuclearities are obtained, including dimeric compounds [Cp*Ln(AlMe4)(μ2-Cl)]2 for the smaller metal centers Ln = Ho, Er, iodido-bridged tetranuclear rings [Cp*Ln(μ2-I)2]4 (Ln = Y, Tb, Dy, Ho, Er), and a heterobimetallic tetramethylaluminato-bridged gadolinium cluster [Cp*4Gd4I7(AlMe4)]2. The tetranuclear dysprosium complex [Cp*Dy(μ2-I)2]4 shows single-molecule magnet (SMM) behavior in zero applied field with an effective energy barrier of 164(10) cm-1.
期刊介绍：
Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.
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