Abstract

The reactions of neutral cage metallophenylsiloxanes [PhSiO₂]₆M₆[PhSiO₂]₆ (M = Cu or Ni) of the sandwich type with alkaline acetylacetonate K(Acac) and of alkaline cage metallosiloxane [PhSiO₂]₁₂Cu₄Na₄ of the globular type with the neutral complex Co(Acac)₂ are studied. Hexanuclear Cu₆- (I) and Ni₆-phenylsiloxanes (II) and octanuclear (Cu₄,Co₄)-phenylsiloxane (III) formed in the reactions are studied by X-ray diffraction analysis (CIF files CCDC nos. 1974285 (I), 1974286 (II), and 1974287 (III)). It is shown that the type of the structure (sandwich or globular) of the initial metallosiloxane is retained in all cases. However, in the case of Ni-siloxane, the coordination with two Acac ligands results in an appreciable shift of the siloxane cycles relative to each other and in the transformation of the usual sandwich characteristic of neutral Ni-phenylsiloxane into a distorted sandwich. The presence of four Acac ligands in globular (Cu₄,Co₄)-phenylsiloxane lead to the elongation of the distance between two linear Cu–Cu fragments of the molecules, which provides the formation of the structure of the “biconvex lens” type.

中文翻译：

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具有乙酰丙酮酸酯配体的金属硅氧烷

摘要

夹心型中性笼状金属苯基硅氧烷[PhSiO ₂ ] ₆ M ₆ [PhSiO ₂ ] ₆ (M = Cu 或 Ni) 与碱性乙酰丙酮 K(Acac) 和碱性笼状金属硅氧烷 [PhSiO ₂ ] ₁₂ Cu ₄ Na _{4 的反应}研究了具有中性配合物 Co(Acac) ₂的球状结构。六核的Cu ₆ - （我）和Ni _6个-phenylsiloxanes（II）和octanuclear（铜₄，钴₄）-phenylsiloxane（III通过 X 射线衍射分析（CIF 文件 CCDC 编号 1974285 ( I )、1974286 ( II ) 和 1974287 ( III )）研究反应中形成的)。结果表明，在所有情况下都保留了初始金属硅氧烷的结构类型（夹心或球状）。然而，在 Ni-硅氧烷的情况下，与两个 Acac 配体的配位导致硅氧烷循环相对于彼此的明显偏移，并将中性 Ni-苯基硅氧烷的通常夹心特性转变为扭曲的夹心。球状中存在四种 Acac 配体 (Cu ₄ ,Co ₄)-苯基硅氧烷导致分子的两个线性 Cu-Cu 片段之间的距离延长，这提供了“双凸透镜”类型结构的形成。