Kevin Woern, Andrey I Poddel'sky, Alex Mayer, Claudio Schrenk, Andreas Schnepf, Svetlana V Klementyeva
{"title":"具有类金属锗簇的环戊二烯镧配合物系列。","authors":"Kevin Woern, Andrey I Poddel'sky, Alex Mayer, Claudio Schrenk, Andreas Schnepf, Svetlana V Klementyeva","doi":"10.1021/acs.inorgchem.4c01082","DOIUrl":null,"url":null,"abstract":"<p><p>A series of cyclopentadienyllanthanum complexes with the disilylated metalloid germanium cluster [Ge<sub>9</sub>(Hyp)<sub>2</sub>]<sup>2-</sup> [Hyp = Si(SiMe<sub>3</sub>)<sub>3</sub>] has been prepared and fully characterized. The synthetic procedure is based on the salt metathesis reaction of two different cyclopentadienyllanthanum diiodides CpLaI<sub>2</sub> (Cp: Cp*, pentamethylcyclopentadienyl; Cp<sup>ttt</sup>, 1,2,4-tri-<i>tert</i>-butylcyclopentadienyl) with K<sub>2</sub>[Ge<sub>9</sub>(Hyp)<sub>2</sub>] in tetrahydrofuran (THF) with a subsequent extraction with <i>n</i>-hexane. The composition of the obtained compounds and the mode of coordination of the germanium cluster to the rare-earth metal are strongly influenced by the steric demand of the cyclopentadienyl ligands and the crystallization conditions. The centrosymmetric dimeric compounds with the common formula [CpLa(solv)(η<sup>2,3</sup>-Ge<sub>9</sub>(Hyp)<sub>2</sub>)]<sub>2</sub> [<b>1</b>, Cp = Cp*, solv-THF; <b>2</b>, Cp = Cp<sup>ttt</sup>, solv-NCCH<sub>2</sub>C(Me)NSiMe<sub>3</sub>] have been isolated by the slow evaporation of a <i>n</i>-hexane solution, while a mononuclear complex [Cp<sup>ttt</sup>La(THF)<sub>2</sub>(η<sup>3</sup>-Ge<sub>9</sub>(Hyp)<sub>2</sub>)] (<b>4</b>) was found by crystallization from THF. The repeated recrystallization of <b>1</b> from <i>n</i>-hexane afforded the asymmetric dimer [Cp*La(THF)(η<sup>2,3</sup>-Ge<sub>9</sub>(Hyp)<sub>2</sub>)][Cp*La(η<sup>2,3</sup>-Ge<sub>9</sub>(Hyp)<sub>2</sub>)] (<b>3</b>) with only one coordinated THF molecule.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.3000,"publicationDate":"2024-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"A Series of Cyclopentadienyl Lanthanum Complexes with Metalloid Germanium Clusters.\",\"authors\":\"Kevin Woern, Andrey I Poddel'sky, Alex Mayer, Claudio Schrenk, Andreas Schnepf, Svetlana V Klementyeva\",\"doi\":\"10.1021/acs.inorgchem.4c01082\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>A series of cyclopentadienyllanthanum complexes with the disilylated metalloid germanium cluster [Ge<sub>9</sub>(Hyp)<sub>2</sub>]<sup>2-</sup> [Hyp = Si(SiMe<sub>3</sub>)<sub>3</sub>] has been prepared and fully characterized. The synthetic procedure is based on the salt metathesis reaction of two different cyclopentadienyllanthanum diiodides CpLaI<sub>2</sub> (Cp: Cp*, pentamethylcyclopentadienyl; Cp<sup>ttt</sup>, 1,2,4-tri-<i>tert</i>-butylcyclopentadienyl) with K<sub>2</sub>[Ge<sub>9</sub>(Hyp)<sub>2</sub>] in tetrahydrofuran (THF) with a subsequent extraction with <i>n</i>-hexane. The composition of the obtained compounds and the mode of coordination of the germanium cluster to the rare-earth metal are strongly influenced by the steric demand of the cyclopentadienyl ligands and the crystallization conditions. The centrosymmetric dimeric compounds with the common formula [CpLa(solv)(η<sup>2,3</sup>-Ge<sub>9</sub>(Hyp)<sub>2</sub>)]<sub>2</sub> [<b>1</b>, Cp = Cp*, solv-THF; <b>2</b>, Cp = Cp<sup>ttt</sup>, solv-NCCH<sub>2</sub>C(Me)NSiMe<sub>3</sub>] have been isolated by the slow evaporation of a <i>n</i>-hexane solution, while a mononuclear complex [Cp<sup>ttt</sup>La(THF)<sub>2</sub>(η<sup>3</sup>-Ge<sub>9</sub>(Hyp)<sub>2</sub>)] (<b>4</b>) was found by crystallization from THF. The repeated recrystallization of <b>1</b> from <i>n</i>-hexane afforded the asymmetric dimer [Cp*La(THF)(η<sup>2,3</sup>-Ge<sub>9</sub>(Hyp)<sub>2</sub>)][Cp*La(η<sup>2,3</sup>-Ge<sub>9</sub>(Hyp)<sub>2</sub>)] (<b>3</b>) with only one coordinated THF molecule.</p>\",\"PeriodicalId\":40,\"journal\":{\"name\":\"Inorganic Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":4.3000,\"publicationDate\":\"2024-07-10\",\"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.4c01082\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"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.4c01082","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
A Series of Cyclopentadienyl Lanthanum Complexes with Metalloid Germanium Clusters.
A series of cyclopentadienyllanthanum complexes with the disilylated metalloid germanium cluster [Ge9(Hyp)2]2- [Hyp = Si(SiMe3)3] has been prepared and fully characterized. The synthetic procedure is based on the salt metathesis reaction of two different cyclopentadienyllanthanum diiodides CpLaI2 (Cp: Cp*, pentamethylcyclopentadienyl; Cpttt, 1,2,4-tri-tert-butylcyclopentadienyl) with K2[Ge9(Hyp)2] in tetrahydrofuran (THF) with a subsequent extraction with n-hexane. The composition of the obtained compounds and the mode of coordination of the germanium cluster to the rare-earth metal are strongly influenced by the steric demand of the cyclopentadienyl ligands and the crystallization conditions. The centrosymmetric dimeric compounds with the common formula [CpLa(solv)(η2,3-Ge9(Hyp)2)]2 [1, Cp = Cp*, solv-THF; 2, Cp = Cpttt, solv-NCCH2C(Me)NSiMe3] have been isolated by the slow evaporation of a n-hexane solution, while a mononuclear complex [CptttLa(THF)2(η3-Ge9(Hyp)2)] (4) was found by crystallization from THF. The repeated recrystallization of 1 from n-hexane afforded the asymmetric dimer [Cp*La(THF)(η2,3-Ge9(Hyp)2)][Cp*La(η2,3-Ge9(Hyp)2)] (3) with only one coordinated THF molecule.
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.