Selective hydrosiloxane synthesis via dehydrogenative coupling of silanols with hydrosilanes catalysed by Fe complexes bearing a tetradentate PNNP ligand
Selective hydrosiloxane synthesis via dehydrogenative coupling of silanols with hydrosilanes catalysed by Fe complexes bearing a tetradentate PNNP ligand
复制标题
带有四齿 PNNP 配体的 Fe 配合物催化硅烷醇与氢硅烷脱氢偶联选择性氢硅氧烷合成
DOI：
10.1039/c8dt04168g
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发表时间：
2018
影响因子：
4
通讯作者：
Nakajima Yumiko
中科院分区：
文献类型：
--
作者：
Takeshita Tomohiro;Sato Kazuhiko;Nakajima Yumiko
使用 PNNP-R（R = Ph 和 Cy）作为具有刚性经向四齿结构的强 σ 供体配体，建立了明确的铁配合物系统。通过相应的二卤化铁与NaBEt3H反应合成了反应性Fe(0)配合物[{Fe(PNNP-R)}2(μ-N2)]并进行了结构表征。该反应通过二氢化铁中间体 [Fe(H)2(PNNP-R)] 进行，该中间体经过 H2 还原消除，支持 PNNP-R 的半不稳定行为。 [{Fe(PNNP-R)}2(μ-N2)]催化硅烷醇与硅烷的脱氢偶联，选择性地形成各种氢硅氧烷，这是合成一系列硅氧烷化合物的重要组成部分。该系统表现出比先前报道的贵金属催化系统更高的催化效率。
A well-defined iron complex system was established using PNNP-R (R = Ph and Cy) as a strong σ-donating ligand with a rigid meridional tetradentate structure. Reactive Fe(0) complexes [{Fe(PNNP-R)}2(μ-N2)] were synthesized by a reaction of the corresponding iron dihalide with NaBEt3H and structurally characterized. The reaction proceeded via the iron dihydride intermediate [Fe(H)2(PNNP-R)], which underwent H2 reductive elimination, supporting the hemilabile behavior of PNNP-R. [{Fe(PNNP-R)}2(μ-N2)] catalyzed the dehydrogenative coupling of silanols with silanes to selectively form various hydrosiloxanes, which are important building blocks for the synthesis of a range of siloxane compounds. This system exhibited higher catalytic efficiency than the previously reported precious-metal-catalyzed systems.