Interdisciplinary Research Centre for Catalytic Chemistry (IRC3), National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba Central 5, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan.
Dalton Trans. 2018 Dec 21;47(47):17004-17010. doi: 10.1039/c8dt04168g. Epub 2018 Nov 21.
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)}(μ-N)] were synthesized by a reaction of the corresponding iron dihalide with NaBEtH and structurally characterized. The reaction proceeded via the iron dihydride intermediate [Fe(H)(PNNP-R)], which underwent H reductive elimination, supporting the hemilabile behavior of PNNP-R. [{Fe(PNNP-R)}(μ-N)] 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.
采用 PNNP-R（R=Ph 和 Cy）作为强 σ-给体配体，具有刚性轴向四齿配位结构，建立了一个明确的铁配合物体系。通过相应的铁二卤化物与 NaBEtH 的反应，合成了反应性 Fe(0)配合物[{Fe(PNNP-R)}（μ-N)]，并对其进行了结构表征。反应通过铁二氢化物中间体[Fe(H)(PNNP-R)]进行，该中间体经历 H 还原消除，支持了 PNNP-R 的半配位行为。[{Fe(PNNP-R)}（μ-N)]催化硅醇与硅烷的脱氢偶联，选择性地形成各种硅氧烷，这些硅氧烷是合成一系列硅氧烷化合物的重要构建块。该体系的催化效率高于先前报道的贵金属催化体系。
