碳二亚胺与二价镧系元素物种的对比反应
Contrasting Reactions of Carbodiimides with Divalent Lanthanoid Species.
作者信息
Vithana Vidushi P, Guo Zhifang, Deacon Glen B, Junk Peter C
机构信息
College of Science & Engineering, James Cook University, Townsville, Queensland, 4811, Australia.
School of Chemistry, Monash University, Clayton, Victoria, 3800, Australia.
出版信息
Chemistry. 2025 May 19;31(28):e202500759. doi: 10.1002/chem.202500759. Epub 2025 Apr 9.
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(OAr)(thf)]·PhMe with N,N'-diisopropylcarbodiimide (iPrNCNiPr) resulted in the formation of the oxalamidinatosamarium(III) complex [(OArEt)₂Sm(μ-C₂N₄iPr₄)Sm(OAr)₂]·2PhMe (1). In contrast, the use of the bulkier N,N'-dicyclohexylcarbodiimide (CyNCNCy) led to the formation of a formamidinatosamarium(III) complex [Sm(OAr)(CyNC(H)NCy)(thf)]⋅2thf (2). Reactions between rare earth metals (RE = Yb, Eu) with one molar equivalent of bis(phenylethynyl)mercury (Hg(PhCC)) and two molar equivalents of N,N'-dicyclohexylcarbodiimide (CyNCNCy) in tetrahydrofuran (thf) at room temperature yielded lanthanoid C-phenylethynylamidinate complexes, trivalent [Yb{CyNC(C≡CPh)NCy}]·2thf (3) and divalent [Eu{CyNC(C≡CPh)NCy}₂(thf)₂] (4). [Sm(OAr)(thf)].PhMe was obtained from SmI(thf) and the in situ generated potassium aryl oxide and is a five-coordinate monomer with a stereochemistry between trigonal bipyramidal and square pyramidal.
镧系元素物种与碳二亚胺（RN═C═NR'）的反应表现出相当大的多样性。因此，用N，N'-二异丙基碳二亚胺（iPrNCNiPr）处理二价的2,6-二叔丁基-4-乙基苯酚钐配合物[Sm（OAr）（thf）]·PhMe，得到草酰胺基钐（III）配合物[（OArEt）₂Sm（μ-C₂N₄iPr₄）Sm（OAr）₂]·2PhMe（1）。相比之下，使用体积更大的N，N'-二环己基碳二亚胺（CyNCNCy）则导致甲脒基钐（III）配合物[Sm（OAr）（CyNC（H）NCy）（thf）]⋅2thf（2）的形成。在室温下，稀土金属（RE = Yb，Eu）与一摩尔当量的双（苯乙炔基）汞（Hg（PhCC））和两摩尔当量的N，N'-二环己基碳二亚胺（CyNCNCy）在四氢呋喃（thf）中反应，生成镧系元素的C-苯乙炔基脒配合物，三价的[Yb{CyNC（C≡CPh）NCy}]·2thf（3）和二价的[Eu{CyNC（C≡CPh）NCy}₂（thf）₂]（4）。[Sm（OAr）（thf）].PhMe由SmI（thf）和原位生成的芳基氧化钾制得，是一种五配位单体，其立体化学介于三角双锥和四方锥之间。
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