Phosphinodi(benzylsilane) PhP{(o‑C6H4CH2)SiMe2H}2: A Versatile “PSi2Hx” Pincer-Type Ligand at Ruthenium
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https://figshare.com/articles/dataset/Phosphinodi_benzylsilane_PhP_i_o_i_C_sub_6_sub_H_sub_4_sub_CH_sub_2_sub_SiMe_sub_2_sub_H_sub_2_sub_A_Versatile_PSi_sub_2_sub_H_sub_i_x_i_sub_Pincer_Type_Ligand_at_Ruthenium/2381878
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资源简介：
The synthesis of the new phosphinodi(benzylsilane) compound PhP{(o-C6H4CH2)SiMe2H}2 (1) is achieved in a one-pot reaction from the corresponding phenylbis(o-tolylphosphine). Compound 1 acts as a pincer-type ligand capable of adopting different coordination modes at Ru through different extents of Si–H bond activation as demonstrated by a combination of X-ray diffraction analysis, density functional theory calculations, and multinuclear NMR spectroscopy. Reaction of 1 with RuH2(H2)2(PCy3)2 (2) yields quantitatively [RuH2{[η2-(HSiMe2)-CH2-o-C6H4]2PPh}(PCy3)] (3), a complex stabilized by two rare high order ε-agostic Si–H bonds and involved in terminal hydride/η2-Si–H exchange processes. A small free energy of reaction (ΔrG298 = +16.9 kJ mol–1) was computed for dihydrogen loss from 3 with concomitant formation of the 16-electron species [RuH{[η2-(HSiMe2)-CH2-o-C6H4]PPh[CH2-o-C6H4SiMe2]}(PCy3)] (4). Complex 4 features an unprecedented 29Si NMR decoalescence process. The dehydrogenation process is fully reversible under standard conditions (1 bar, 298 K).
创建时间：
2016-02-18
