...
  • 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>Organometallics >Synthesis, Structure, and Reactivity of Osmium Silyl and Silylene Complexes Cp(Me_3P)_2OsSiR_2X and [Cp(Me_3P)_2OsSiR_2][B(C_6F_5)_4] (R = Me, ~iPr; X = Cl, OTf)
【24h】

Synthesis, Structure, and Reactivity of Osmium Silyl and Silylene Complexes Cp(Me_3P)_2OsSiR_2X and [Cp(Me_3P)_2OsSiR_2][B(C_6F_5)_4] (R = Me, ~iPr; X = Cl, OTf)

机译：Sil甲硅烷基和亚甲硅烷基络合物Cp（Me_3P）_2OsSiR_2X和[Cp（Me_3P）_2OsSiR_2] [B（C_6F_5）_4]的合成，结构和反应性（R = Me，〜iPr; X = Cl，OTf）

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

Reaction of Cp(Me_3P)_2OsCH_2SiMe_3 (1, Cp = C_5Me_5) with an excess of ~IPr_2Si(H)Cl afforded Cp(Me_3P)_2OsSi~iPr_2Cl (2) in good yield, without the formation of Os(IV) products. Treatment of 2 with Me_3SiOTf (OTf = triflate, OSO_2CF_3) afforded the corresponding triflatosilyl complex Cp(Me_3P)_2OsSi~iPr_2OTf (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(Me_3P)_2OsSiMe_2X (X = Cl (4), OTf (5)). Complexes 2-5 were converted to the corresponding base-free silylene complexes [Cp(Me_3P)_2Os=SiR_2] [B(C_6F_5)_4] (R = Me (6), ~iPr (7)) by anion metathesis with Li[B(C_6F_5)_4]·3Et_2O. 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 ~(29)Si NMR resonances that are shifted to very low field (350 ppm for 6; 363 ppm for 7). The spectroscopic and structural differences between these silylene complexes and their precursors are discussed. While stable in fluorobenzene, 6 and 7 are rapidly oxidized by chlorocarbons via a radical pathway to form cationic Os(III) chlorosilyl species. Reactions of 7 with oxygen atom sources such as N_2O and 2-picoline N-oxide afforded the N_2-bridged diosmium complex [Cp(Me_3P)_2Os-NN-Os(PMe_3)_2Cp] [B(C_6F_5)_4]_2 (8) and the cyclic siloxane (OSi~iPr_2)_3. Reaction of 7 with elemental sulfur provided the turquoise, S_2-bridged diosmium complex [Cp(Me_3P)_2Os-S-S-Os(PMe_3)_2Cp][B(C_6F_5)_4]_2 (9) and unidentified silicon-containing products.
机译：Cp（Me_3P）_2OsCH_2SiMe_3（1，Cp = C_5Me_5）与过量的〜IPr_2Si（H）Cl反应生成Cp（Me_3P）_2OsSi〜iPr_2Cl（2）且产率高，而没有形成Os（IV）产物。用Me_3SiOTf（OTf =三氟甲磺酸盐，OSO_2CF_3）处理2得到相应的三氟甲硅烷基络合物Cp（Me_3P）_2OsSi〜iPr_2OTf（3），根据结构和光谱测量，该化合物似乎具有重要的甲硅烷基特征。这些络合物的合成途径类似于先前报道的二甲基甲硅烷基化合物Cp（Me_3P）_2OsSiMe_2X（X = Cl（4），OTf（5））。通过与Li [的阴离子复分解反应，将配合物2-5转换为相应的无碱亚甲硅烷基配合物[Cp（Me_3P）_2Os = SiR_2] [B（C_6F_5）_4]（R = Me（6），〜iPr（7））。 B（C_6F_5）_4]·3Et_2O。 6和7均通过多核NMR光谱和X射线晶体学表征。甲硅烷基络合物具有硅的三角形平面环境，短的Os-Si接触（6时为2.257（7）A，7时为2.263（1）A）和〜（29）Si NMR共振，这些共振已转移到非常低的电场（ 350 ppm（6）; 363 ppm（7）。讨论了这些亚甲硅烷基络合物及其前体之间的光谱和结构差异。虽然在氟苯中稳定，但6和7会通过自由基途径被氯代烃迅速氧化，形成阳离子Os（III）氯甲硅烷基。 7与氧原子源（例如N_2O和2-picoline N-氧化物）的反应提供了N_2桥连的di络合物[Cp（Me_3P）_2Os-NN-Os（PMe_3）_2Cp] [B（C_6F_5）_4] _2（8）和环状硅氧烷（OSi〜iPr_2）_3。 7与元素硫的反应提供了绿松石，S_2桥接的di络合物[Cp（Me_3P）_2Os-S-S-Os（PMe_3）_2Cp] [B（C_6F_5）_4] _2（9）和未确定的含硅产物。

著录项

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号