((t-Bu2PCH2SiMe2)2N)RuCl | 574703-69-8

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: ((t-Bu2PCH2SiMe2)2N)RuCl
• 英文别名: bis[ditert-butylphosphanylmethyl(dimethyl)silyl]azanide;chlororuthenium(1+)
• CAS: 574703-69-8
• 化学式: C₂₂H₅₂ClNP₂RuSi₂
• 分子量: 585.303
• InChiKey: AYKCZWBCICUAMD-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  碘代三甲硅烷 、 ((t-Bu2PCH2SiMe2)2N)RuCl 以 甲苯 为溶剂， 以83%的产率得到bis[ditert-butylphosphanylmethyl(dimethyl)silyl]azanide;iodoruthenium(1+)
  参考文献：
  名称：

  [(^tBu₂PCH₂SiMe₂)₂N]RuMe₂:  Synthesis and Reactivity of an Unsaturated Ruthenium Dialkyl Radical Species

  摘要：

  The reaction of PNPRuCl (PNP = ((Bu2PCH2SiMe2)-Bu-iota)(2)N-) with excess MeLi at -78 degrees C, followed by addition of a one-electron oxidant, leads to the thermally stable (at 25 degrees C), low-spin, five-coordinate trivalent ruthenium complex PNPRuMe2, 1. For comparison PNPRuI2, 2, was also synthesized and shown equally to be a low-spin d(5) complex. Compound 1 reacts with NO to produce the diamagnetic ruthenium(II) complex PNPRuMe2(NO), 3, with H-2 to give PNPRu(H)(3), 5, and with excess CO to produce PNPRu(COMe)CO, 6. The unusual stability of 1 is suggested to arise from the steric encapsulation of the radical center provided by the extremely bulky pincer ligand, the low coordination number (5), and a non-redox-innocent amide functionality.

  DOI：

  10.1021/om0508536
• 作为产物：
  描述：

  [((t-Bu2PCH2SiMe2)2N)Ru(NPh)][((t-Bu2PCH2SiMe2)2N)RuCl3] 在 zinc 作用下， 以 氘代四氢呋喃 为溶剂， 生成 ((t-Bu2PCH2SiMe2)2N)RuCl 、 ((t-Bu2PCH2SiMe2)2N)Ru(NPh)
  参考文献：
  名称：

  金属轨道占有率和主量子数对有机叠氮化物（RN3）向过渡金属酰亚胺配合物转化的影响。

  摘要：

  叠氮化苯与（PNP）Ni的反应（其中PNP =（（t）Bu 2PCH 2SiMe 2）2N（-））迅速生成N 2并在产物（PNP = NPh）Ni（I ）。与（PNP）FeCl的类似反应继续形成P = N键，但没有N 2放出，从而提供（PNP = NN = NPh）FeCl。与（PNP）RuCl的类似反应会发生，金属处的氧化还原变化更为明显（并且会释放N 2），从而生成由（PNP）Ru（NPh）（+）和（PNP）RuCl 3（-）组成的盐，以及等摩尔（PNP）Ru（NPh）。这些结果之间的对比可用来推断哪些条件有利于N 2损失以及将PhN 3中的NPh片段氧化结合到金属络合物中。

  DOI：

  10.1021/ic801035z

文献信息

• An evaluation of monovalent osmium supported by the PNP ligand environment
  作者：Nikolay Tsvetkov、Hongjun Fan、Kenneth G. Caulton

  DOI：10.1039/c0dt00989j

  日期：——

  Nitrogen is essential to reaction of (PNP)OsI (PNP is N(SiMe2CH2PtBu2)2) and Mg powder in THF, to give equimolar (PNP)OsH(N2) and hydrido carbene [(tBu2PCH2SiMe2)N(SiMe2CH2PtBu(CMe2CH)]OsH. This reaction is attributed to H2 evolution from solid magnesium, rather than high energy H atom transfer between molecules, but relies also on the strong π-basicity of Os in favoring α-H migration from the metallated tBu group on Os to form the second product, the hydrido carbene species. The path to two different products begins because the simple N2 adduct of (PNP)OsI undergoes spontaneous heterolytic H–C splitting of the tBu methyl group, to produce a secondary amine intermediate [(tBu2PCH2SiMe2)N(H)(SiMe2CH2PtBu(CMe2CH2)]OsI(N2) which can then be dehydrohalogenated by Mg. The analogous reaction for (PNP)RuCl shows production of only (PNP)RuH(N2), with none of the hydride carbene dehydrogenation product. Comparative (Ruvs. Os) DFT calculations reveal the reaction steps where the Os analog is much more exothermic, accounting for certain reaction selectivities.

  氮是 (PNP)OsI （PNP 为 N(SiMe2CH2PtBu2)2）和镁粉在四氢呋喃中发生反应的必要条件，反应生成等摩尔 (PNP)OsH(N2) 和碳氢化物 [(tBu2PCH2SiMe2)N(SiMe2CH2PtBu(CMe2CH)]OsH。这一反应归因于从固体镁中演化出的 H2，而不是分子间的高能 H 原子转移，但也依赖于 Os 的强π碱性，有利于 α-H 从 Os 上的金属化 tBu 基团迁移，形成第二种产物，即碳化氢。通向两种不同产物的路径开始于 (PNP)OsI 的简单 N2 加合物自发地发生 tBu 甲基的异解 H-C 分裂，生成仲胺中间体[(tBu2PCH2SiMe2)N(H)(SiMe2CH2PtBu(CMe2CH2)]OsI(N2)，然后可由 Mg 进行脱氢卤化。(PNP)RuCl 的类似反应只生成 (PNP)RuH(N2)，没有碳氢化合物脱氢产物。比较（Ruvs. Os）DFT 计算揭示了 Os 类似物放热更多的反应步骤，从而解释了某些反应的选择性。
• [(^tBu₂PCH₂SiMe₂)₂N]RuCH₃:  The Origin of Extremely Facile, Double H−C(sp³) Activation Generating a “Hydrido-Carbene” Complex
  作者：Michael J. Ingleson、Xiaofan Yang、Maren Pink、Kenneth G. Caulton

  DOI：10.1021/ja052973a

  日期：2005.8.1

  The four-coordinate compound [(tBu2PCH2SiMe2)2N]RuCH3 undergoes rapid double H-C(sp3) activation at -78 degrees C to generate a "hydrido-carbene" complex. DFT calculations suggest that the origin of the low barrier to methane elimination is an alpha-agostic interaction in the low-lying singlet state of the highly unsaturated (PNP)RuMe. The hydrido-carbene complex can be viewed as a "masked" resting state of the four-coordinate cyclometalated alkyl complex, [(tBu2PCH2SiMe2)N(Me2SiCH2P(tBu)(C(CH3)2CH2)]Ru, where hydride migration from metal to carbon occurs before any subsequent reactivity.