Synthesis, Structure, and Reactivity of Osmium Silyl and Silylene Complexes Cp*(Me3P)2OsSiR2X and [Cp*(Me3P)2OsSiR2][B(C6F5)4] (R = Me, iPr; X = Cl, OTf)
Synthesis, Structure, and Reactivity of Osmium Silyl and Silylene Complexes Cp*(Me3P)2OsSiR2X and [Cp*(Me3P)2OsSiR2][B(C6F5)4] (R = Me, iPr; X = Cl, OTf)
复制标题
锇甲硅烷基和甲硅烷基配合物 Cp*(Me3P)2OsSiR2X 和 [Cp*(Me3P)2OsSiR2][B(C6F5)4] (R = Me, iPr; X = Cl, OTf) 的合成、结构和反应性
DOI：
10.1021/om0341808
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发表时间：
2004
期刊：
影响因子：
2.8
通讯作者：
T. Tilley
中科院分区：
文献类型：
--
作者：
P. Glaser;Paulus W. Wanandi;T. Tilley
Cp*（Me_3P）_2OsCH_2SiMe_3（1，Cp* = C_5Me_5）与过量的iPr_2Si（H）Cl反应，以良好的产率得到Cp*（Me_3P）_2OsSiiPr_2Cl（2），没有生成Os（IV）产物.用Me 3SiOTf（OTf = triflate，OSO 2CF 3）处理2，得到相应的三氟甲硅烷基配合物Cp*（Me 3 P）2 OsSiiPr 2 OTf（3），通过结构和光谱测定，它似乎具有明显的亚甲硅烷基特征。这些配合物的合成路线类似于先前报道的二甲基甲硅烷基化合物Cp*（Me 3 P）2 OsSiMe 2X（X = Cl（4），OTf（5））所采用的合成路线。配合物2 - 5通过与Li[B（C6 F5）4]·3Et 2 O的阴离子复分解转化为相应的无碱亚甲硅烷基配合物[Cp*（Me 3 P）2 OsSiR 2][B（C6 F5）4]（R = Me（6），iPr（7））。6和7都通过多核NMR光谱和X射线晶体学进行了表征。亚甲硅烷基配合物具有硅的三角平面环境，短的Os−Si接触（6为2.257（7）A，7为2.263（1）A），以及29 Si NMR共振，这些共振是移位的。
Reaction of Cp*(Me3P)2OsCH2SiMe3 (1, Cp* = C5Me5) with an excess of iPr2Si(H)Cl afforded Cp*(Me3P)2OsSiiPr2Cl (2) in good yield, without the formation of Os(IV) products. Treatment of 2 with Me3SiOTf (OTf = triflate, OSO2CF3) afforded the corresponding triflatosilyl complex Cp*(Me3P)2OsSiiPr2OTf (3), which appears to possess substantial silylene character, as determined by structural and spectroscopic measurements. The synthetic route to these complexes is analogous to that employed for the previously reported dimethylsilyl compounds Cp*(Me3P)2OsSiMe2X (X = Cl (4), OTf (5)). Complexes 2−5 were converted to the corresponding base-free silylene complexes [Cp*(Me3P)2OsSiR2][B(C6F5)4] (R = Me (6), iPr (7)) by anion metathesis with Li[B(C6F5)4]·3Et2O. Both 6 and 7 were characterized by multinuclear NMR spectroscopy and X-ray crystallography. The silylene complexes feature a trigonal planar environment for silicon, short Os−Si contacts (2.257(7) A for 6, 2.263(1) A for 7), and 29Si NMR resonances that are shift...