Vidushi P. Vithana, Zhifang Guo, Glen B. Deacon, Peter C. Junk
{"title":"碳二亚胺与二价类镧的对比反应。","authors":"Vidushi P. Vithana, Zhifang Guo, Glen B. Deacon, Peter C. Junk","doi":"10.1002/chem.202500759","DOIUrl":null,"url":null,"abstract":"<p>Reactions of lanthanoid species with carbodiimides (RN ═ C ═ NR′) show considerable variety. Thus, treatment of the divalent 2,6-di-<i>tert</i>-butyl-4-ethylphenolatosamarium complex, [Sm(OAr<sup>Et</sup>)<sub>2</sub>(thf)<sub>3</sub>]·PhMe with <i>N</i>,<i>N</i>'-diisopropylcarbodiimide (<i>i</i>PrNCN<i>i</i>Pr) resulted in the formation of the oxalamidinatosamarium(III) complex [(OArEt)₂Sm(μ-C₂N₄<i>i</i>Pr₄)Sm(OAr<sup>Et</sup>)₂]·2PhMe (1). In contrast, the use of the bulkier <i>N</i>,<i>N'</i>-dicyclohexylcarbodiimide (CyNCNCy) led to the formation of a formamidinatosamarium(III) complex [Sm(OAr<sup>Et</sup>)<sub>2</sub>(CyNC(H)NCy)(thf)<sub>2</sub>]⋅2thf <b>(2)</b>. Reactions between rare earth metals (RE = Yb, Eu) with one molar equivalent of bis(phenylethynyl)mercury (Hg(PhCC)<sub>2</sub>) and two molar equivalents of <i>N</i>,<i>N</i>'-dicyclohexylcarbodiimide (CyNCNCy) in tetrahydrofuran (thf) at room temperature yielded lanthanoid <i>C</i>-phenylethynylamidinate complexes, trivalent [Yb<sup>III</sup>{CyNC(C≡CPh)NCy}<sub>3</sub>]·2thf <b>(3)</b> and divalent [Eu{CyNC(C≡CPh)NCy}₂(thf)₂] <b>(4)</b>. [Sm(OAr<sup>Et</sup>)<sub>2</sub>(thf)<sub>3</sub>].PhMe was obtained from SmI<sub>2</sub>(thf)<sub>2</sub> and the in situ generated potassium aryl oxide and is a five-coordinate monomer with a stereochemistry between trigonal bipyramidal and square pyramidal.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":"31 28","pages":""},"PeriodicalIF":3.7000,"publicationDate":"2025-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/chem.202500759","citationCount":"0","resultStr":"{\"title\":\"Contrasting Reactions of Carbodiimides with Divalent Lanthanoid Species\",\"authors\":\"Vidushi P. Vithana, Zhifang Guo, Glen B. Deacon, Peter C. Junk\",\"doi\":\"10.1002/chem.202500759\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Reactions of lanthanoid species with carbodiimides (RN ═ C ═ NR′) show considerable variety. Thus, treatment of the divalent 2,6-di-<i>tert</i>-butyl-4-ethylphenolatosamarium complex, [Sm(OAr<sup>Et</sup>)<sub>2</sub>(thf)<sub>3</sub>]·PhMe with <i>N</i>,<i>N</i>'-diisopropylcarbodiimide (<i>i</i>PrNCN<i>i</i>Pr) resulted in the formation of the oxalamidinatosamarium(III) complex [(OArEt)₂Sm(μ-C₂N₄<i>i</i>Pr₄)Sm(OAr<sup>Et</sup>)₂]·2PhMe (1). In contrast, the use of the bulkier <i>N</i>,<i>N'</i>-dicyclohexylcarbodiimide (CyNCNCy) led to the formation of a formamidinatosamarium(III) complex [Sm(OAr<sup>Et</sup>)<sub>2</sub>(CyNC(H)NCy)(thf)<sub>2</sub>]⋅2thf <b>(2)</b>. Reactions between rare earth metals (RE = Yb, Eu) with one molar equivalent of bis(phenylethynyl)mercury (Hg(PhCC)<sub>2</sub>) and two molar equivalents of <i>N</i>,<i>N</i>'-dicyclohexylcarbodiimide (CyNCNCy) in tetrahydrofuran (thf) at room temperature yielded lanthanoid <i>C</i>-phenylethynylamidinate complexes, trivalent [Yb<sup>III</sup>{CyNC(C≡CPh)NCy}<sub>3</sub>]·2thf <b>(3)</b> and divalent [Eu{CyNC(C≡CPh)NCy}₂(thf)₂] <b>(4)</b>. [Sm(OAr<sup>Et</sup>)<sub>2</sub>(thf)<sub>3</sub>].PhMe was obtained from SmI<sub>2</sub>(thf)<sub>2</sub> and the in situ generated potassium aryl oxide and is a five-coordinate monomer with a stereochemistry between trigonal bipyramidal and square pyramidal.</p>\",\"PeriodicalId\":144,\"journal\":{\"name\":\"Chemistry - A European Journal\",\"volume\":\"31 28\",\"pages\":\"\"},\"PeriodicalIF\":3.7000,\"publicationDate\":\"2025-03-23\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://onlinelibrary.wiley.com/doi/epdf/10.1002/chem.202500759\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Chemistry - A European Journal\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/chem.202500759\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemistry - A European Journal","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/chem.202500759","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Contrasting Reactions of Carbodiimides with Divalent Lanthanoid Species
Reactions of lanthanoid species with carbodiimides (RN ═ C ═ NR′) show considerable variety. Thus, treatment of the divalent 2,6-di-tert-butyl-4-ethylphenolatosamarium complex, [Sm(OArEt)2(thf)3]·PhMe with N,N'-diisopropylcarbodiimide (iPrNCNiPr) resulted in the formation of the oxalamidinatosamarium(III) complex [(OArEt)₂Sm(μ-C₂N₄iPr₄)Sm(OArEt)₂]·2PhMe (1). In contrast, the use of the bulkier N,N'-dicyclohexylcarbodiimide (CyNCNCy) led to the formation of a formamidinatosamarium(III) complex [Sm(OArEt)2(CyNC(H)NCy)(thf)2]⋅2thf (2). Reactions between rare earth metals (RE = Yb, Eu) with one molar equivalent of bis(phenylethynyl)mercury (Hg(PhCC)2) and two molar equivalents of N,N'-dicyclohexylcarbodiimide (CyNCNCy) in tetrahydrofuran (thf) at room temperature yielded lanthanoid C-phenylethynylamidinate complexes, trivalent [YbIII{CyNC(C≡CPh)NCy}3]·2thf (3) and divalent [Eu{CyNC(C≡CPh)NCy}₂(thf)₂] (4). [Sm(OArEt)2(thf)3].PhMe was obtained from SmI2(thf)2 and the in situ generated potassium aryl oxide and is a five-coordinate monomer with a stereochemistry between trigonal bipyramidal and square pyramidal.
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