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Divalent Europium and Ytterbium Complexes Supported by a Bulky 2-pyridyl Amido Ligand: Synthesis, Structure and Reactivity Studies

Divalent Europium and Ytterbium Complexes Supported by a Bulky 2-pyridyl Amido Ligand: Synthesis, Structure and Reactivity Studies

Ka Wai Ku, Chi Wai Au, Hoi-Shan Chan, Hung Kay Lee

Dalton Trans. 2013 Feb 28;42(8):2841-52.

PMID: 23258130

Abstract:

Metallation of the N-arylated 2-pyridyl amine [HN(C6H3Pr(i)2-2,6)(2-C5H3N-6-Me)] (1) with potassium hydride in Et2O and THF yielded potassium amides [{KL(OEt2)}2] [L = N(C6H3Pr(i)2-2,6)(2-C5H3N-6-Me)] (2) and KL(THF)2 (3), respectively. Treatment of LnI2(THF)2 (Ln = Eu, Yb) with 2 afforded the corresponding Ln(II) amido complexes [EuL(μ-L)2K(THF)] (4) and [YbL2(THF)2] (5). In contrast, an analogous reaction of SmI2(THF)2 with 2 only led to the isolation of homoleptic Sm(III) triamide [SmL3] (6). The reaction chemistry of divalent complexes 4 and 5 was examined. Oxidation of the Eu(II) amido complex 4 by iodine yielded the trivalent [EuL3] (7), whereas addition of Yb(II) diamide 5 to iodine led to the isolation of the bis(amido) Yb(III) iodide complex [YbL2(I)(THF)] (8). Complex 8 could also be prepared by the reaction of 5 with copper(I) iodide. A subsequent reaction of 8 with KOBut gave, unexpectedly, the Yb(III) triamide [YbL3] (9). Reactions of complex 5 with diphenyl dichalcogenides PhEEPh (E = S, Se, Te) also gave [YbL3] (9) as the only isolable product. The solid-state structures of complexes 2 and 4-9 were elucidated by X-ray diffraction analysis.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP19357869	Ytterbium(II) iodide		19357-86-9	Price

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