Redox transmetallation approaches to the synthesis of extremely bulky amido-lanthanoid(ii) and -calcium(ii) complexes†,Dalton Transactions

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Redox transmetallation approaches to the synthesis of extremely bulky amido-lanthanoid(ii) and -calcium(ii) complexes†
Dalton Transactions ( IF 3.5 ) Pub Date : 2018-06-22 00:00:00 , DOI: 10.1039/c8dt02138d
Caspar N. de Bruin-Dickason _{1,

2,

3,

4} , Aaron J. Boutland _{1,

2,

3,

4} , Deepak Dange _{1,

2,

3,

4} , Glen B. Deacon _{1,

2,

3,

4} , Cameron Jones _{1,

2,

3,

4}

Affiliation

Redox transmetallation protolysis reactions between HgPh₂, elemental metals, M = Ca, Eu, or Yb, and the bulkyl arylsilylamine ^PhL^†H (HN(SiPh₃)(Ar^†), Ar^† = C₆H₂Prⁱ{C(H)Ph₂}₂-4,2,6), or the borylsilylamine ^PhL^BoH (HN(SiPh₃){B(DipNCH)₂}, Dip = C₆H₃Prⁱ₂-2,6) pro-ligands yielded complexes incorporating doubly deprotonated, N,C-chelating amido/organyl ligands, viz. [M(L^–H) (thf)_x]_n, L^–H = ^PhL^†–H (1–3) or ^PhL^Bo–H (4–5); M = Ca (1, 4), Eu (2) or Yb (3, 5); x = 0 (5) or 2 (1–4); n = 1 (1–4) or 2 (5). Structural differences between 4 and 5 represent a rare divergence in the chemistry of divalent calcium and ytterbium. Utilisation of a less hindered bis(aryl) amine, ^DL^MH (HN(Dip)(Mes), Mes = C₆H₂Me₃-2,4,6) in a similar reaction yielded a three-coordinate, trigonal planar ytterbium complex [Yb(^DL^M)₂(thf)] (6). Direct redox transmetallation reactions between an amido-mercurial iodide [(^MeL^†)HgI] (7, ^MeL^† = –N(SiMe₃)(Ar^†)) and ytterbium or europium metal afforded homoleptic [Yb(^MeL^†)₂] (8) and heteroleptic [{Eu(^MeL^†)(μ-I)(thf)}₂] (9) respectively. This study highlights the versatility of redox transmetallation pathways to amido-lanthanoid complexes, especially where such compounds are difficult to access using conventional salt metathesis pathways.

中文翻译：

氧化还原金属转移方法可合成非常庞大的酰胺基镧系元素（ii）和-钙（ii）配合物†

HgPh ₂，元素金属M = Ca，Eu或Yb与本体基芳基甲硅烷基胺^Ph L ^† H（HN（SiPh ₃）（Ar ^†），Ar ^† = C ₆ H ₂ Pr ⁱ {C （H）Ph ₂ } ₂ -4,2,6）或硼硅烷基胺^Ph L ^Bo H（HN（SiPh ₃）{B（DipNCH）₂ }，Dip = C ₆ H ₃ Pr ⁱ₂ -2,6）原配体产生结合了双去质子化的N，C的配合物-螯合酰胺/有机基配体，即。[M（L – ^H）（thf）_x ] _n，L ^–H = ^Ph L ^†–H（1-3）或^Ph L ^Bo–H（4–5）；M = Ca（上1，4），铕（2）或镱（3，5）; x = 0（5）或2（1-4）；n = 1（1-4）或2（5）。4和5之间的结构差异代表了二价钙和化学上的罕见差异。在类似的反应中使用受阻较少的双（芳基）胺^D L ^M H（HN（Dip）（Mes），Mes = C ₆ H ₂ Me ₃ -2,4,6）得到三坐标的三边形平面络合物[Yb（^D L ^M）₂（thf）]（6）。酰胺基汞碘化物[（^Me L ^†）HgI]（7，^Me L ^† = –N（SiMe ₃）（Ar ^†））和and或metal金属分别提供了均相[Yb（^Me L ^†）₂ ]（8）和杂合[[Eu（^Me L ^†）（μ-I）（thf）} ₂ ]（9）。这项研究突出了氧化还原金属转移途径对氨基-镧系元素络合物的多功能性，特别是在使用常规盐复分解途径难以获得此类化合物的情况下。

更新日期：2018-06-22

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