ケイ素, １５族元素, 遷移金属からなる高活性シライミンおよびホスファシレン錯体の創製

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  • Construction of Highly Reactive Silanimine- and Phosphasilene-coordinated Complexes Composed of Silicon, Group 15 Elements, and Transition Metals

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<p>η2-Disilene transition-metal complexes have been synthesized by a wide variety of synthetic methods and characterized by X-ray diffraction studies. Their reactivity has been extensively studied so far. However, coordination chemistry of silanimine and phosphasilene, which possess the silicon–nitrogen and silicon–phosphorus double bonds, respectively, has not been well explored, probably due to their instability derived from the polarized silicon–nitrogen and silicon–phosphorus bonds. This review describes the syntheses, structures, and reactivities of η2-silanimine, η1-silanimine, η2-phosphasilene, and η1-phosphasilene complexes, as well as metallosilanimines and metallophosphasilenes. Bonding schemes between transition-metals and silanimine/phosphasilene ligands are mentioned in relation to the Dewar, Chatt, and Duncanson (DCD) model. As related compounds, η2-aminosilyl and η2-phosphinosilyl complexes, which include the three-membered ring composed of transition-metal, silicon, and group 15 elements, are also described. A base-stabilized phosphido(silylene) complex can be postulated as a canonical structure of η2-phosphinosilyl complexes and confirmed by experimental and theoretical studies. η2-Phosphinosilyl complexes would be a good activator of small organic molecules, in which the silicon and phosphorus atoms work cooperatively as a Lewis acid and Lewis base, respectively.</p>

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