Junold Konstantin, Sinner Katharina, Baus Johannes A, Burschka Christian, Fonseca Guerra Célia, Bickelhaupt F Matthias, Tacke Reinhold
Universität Würzburg, Institut für Anorganische Chemie, Am Hubland, 97074 Würzburg (Germany), Fax: (+49) 931-31-84609.
Chemistry. 2014 Dec 8;20(50):16462-6. doi: 10.1002/chem.201404667. Epub 2014 Oct 24.
Reaction of the donor-stabilized silylene 1 (which is three-coordinate in the solid state and four-coordinate in solution) with [HMCp(CO)3 ] (M=Mo, W; Cp=cyclopentadienyl) leads to the cationic five-coordinate silicon(IV) complexes 2 and 3, respectively, and reaction of 1 with CH3 COOH yields the neutral six-coordinate silicon(IV) complex 4. Compounds 2-4 were structurally characterized by crystal structure analyses and multinuclear NMR spectroscopic studies in the solid state and in solution. The formation of 2-4 can be formally described in terms of a Brønsted acid/base reaction, coupled with a redox process (Si(II) →Si(IV) , H(+) →H(-) ).
供体稳定的硅烯1(在固态中为三配位,在溶液中为四配位)与[HMCp(CO)₃](M = Mo、W;Cp = 环戊二烯基)反应,分别生成阳离子五配位硅(IV)配合物2和3,且1与CH₃COOH反应生成中性六配位硅(IV)配合物4。通过晶体结构分析以及固态和溶液中的多核NMR光谱研究对化合物2 - 4进行了结构表征。2 - 4的形成可以形式上用布朗斯特酸/碱反应并结合氧化还原过程(Si(II) → Si(IV),H⁺ → H⁻)来描述。