Abstract

Deprotonation of SiMe₂(HNPbt)₂ proligand (1) by Li(NTms₂) (Tms = SiMe₃) base results in the formation of SiMe₂(LiNPbt)₂ (Pbt = 2-(1,3-benzothiazol-2-yl)phenyl) in solution, which further reacts with GdCl₃ yielding [Li(THF)₄][Gd(SiMe₂(NPbt)₂)₂] complex (2). In an attempt to obtain 2 with the use of n-butyllithium as a base, an unexpected product with an intricate structure - [Gd{Me₂Si(NPbt)(o-NC₆H₄-C(Bu)₂(o-NHC₆H₄S))}(μ-NHPbt)Li(THF)] complex (3) is isolated and structurally characterized. The thiazole ring of one of the substituents of the silandiamide ligand is open in it, while two butyl groups are attached to the thiazole C2 carbon atom. In the reaction of 1 with an excess of butyllithium and YCl₃, a product with the ligand also containing the C(Bu)₂ moiety is formed, which is shown by ¹H NMR. Apart from it, double complex salt [Li(THF)₄][Y(SiMe₂(NPbt)₂)₂] (4) crystallized as a solvate with Et₂O is isolated from the reaction mixture. In an attempt to obtain a monosubstituted [Y(SiMe₂(NPbt))Cl] complex, compound 4·2THF forms along with several crystals of [{Y(SiMe₂(NPbt)₂)}₂(μ-OBu)₂] complex (5) the structure of which is characterized by single crystal X-ray diffraction. The photophysical properties of compound 2 are studied in the THF solution and in the crystalline state.

中文翻译：

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具有 N-苯基苯并噻唑取代基的镧系元素硅烷二酰胺配合物：合成、意外产物、结构和发光

摘要

Li(NTms ₂ ) (Tms = SiMe ₃ ) 碱对SiMe 2 (HNPbt) 2 配体 (1) 进行去质子化_，形成_SiMe 2 ( LiNPbt ₎ 2 ₍ Pbt = 2-(1,3-苯并噻唑-2-)基)苯基)在溶液中，进一步与GdCl ₃反应生成[Li(THF) ₄ ][Gd(SiMe ₂ (NPbt) ₂ ) ₂ ]络合物( 2 )。在尝试以正丁基锂为碱获得2时，意外得到了结构复杂的产物 - [Gd{Me ₂ Si(NPbt)( o -NC ₆ H ₄ -C(Bu) ₂ ( o - NHC ₆ H ₄ S))}(μ-NHPbt)Li(THF)]络合物( 3 )被分离并进行结构表征。硅烷二酰胺配体的取代基之一的噻唑环在其中是开放的，而两个丁基连接至噻唑C2碳原子。在1与过量的丁基锂和YCl ₃的反应中，形成了配体也含有C(Bu) _{2部分的产物，这由}¹ H NMR显示。除此之外，从反应混合物中分离出与Et ₂ O作为溶剂化物结晶的复配盐[Li(THF) ₄ ][Y(SiMe ₂ (NPbt) ₂ ) ₂ ]( 4 )。为了获得单取代的 [Y(SiMe ₂ (NPbt))Cl] 配合物，化合物4 ·2THF 与几个 [{Y(SiMe ₂ (NPbt) ₂ )} ₂ (μ-OBu) ₂ ]晶体一起形成配合物( 5 )，其结构通过单晶X射线衍射表征。研究了化合物2在 THF 溶液和结晶状态下的光物理性质。