TpOs[N(Ph)(BPh2)]Cl2 | 330945-70-5

• 英文名称: TpOs[N(Ph)(BPh2)]Cl2
• 英文别名: (hydrotris(1-pyrazolyl)borate)Os[N(Ph)(BPh2)]Cl2；(hydrotris(pyrazolyl)borate)Os(N(Ph)BPh2)Cl2；TpOs(N(Ph)BPh2)Cl2；[(hydrotris(pyrazolyl)borate)Os(NPhBPh2)Cl2]
• CAS: 330945-70-5
• 化学式: C₂₇H₂₅B₂Cl₂N₇Os
• 分子量: 730.27
• InChiKey: JDXLKCBMFGZAQI-UHFFFAOYSA-L

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：

  TpOs[N(Ph)(BPh2)]Cl2 、 水 在 air 作用下， 以 neat (no solvent, solid phase) 为溶剂， 生成 TpOs(NHPh)Cl2
  参考文献：
  名称：

  在 TpOs(N)Cl2 中将芳基碳负离子添加到亲电氮化配体中形成 CN 键

  摘要：

  锇 (VI) 氮化物复合物 TpOs(N)Cl(2) (1) 已从 K[Os(N)O(3)] 和 KTp 在乙醇 HCl 中制备。它与 PhMgCl 和相关试剂快速反应，将苯基转移到氮化配体上。这形成了 Os(IV) 金属-analido 络合物，它们很容易质子化以得到 analido 络合物 TpOs(NHPh)Cl(2) (4)。硝基苯基衍生物 TpOs(N)PhCl 和 TpOs(N)Ph(2) 与 PhMgCl 的反应速度较慢，并且不是 1 与 PhMgCl 反应的合格中间体。1 与烷基硼烷和芳基硼烷的反应类似地导致一个有机基团转移到氮上，从而产生可分离的硼酰氨基络合物，例如 TpOs[N(Ph)(BPh(2))]Cl(2) (11)。这是前所未有的将氮化配体插入硼-碳键。11水解得到4。机理研究表明，格氏反应和硼烷反应都是通过 Mg 或 B 与氮化配体的初始弱配位，然后碳负离子迁

  DOI：

  10.1021/ja0028424
• 作为产物：
  描述：

  [(hydrotris(pyrazolyl)borate)Os(N)Cl2] 、 三苯基硼烷 以 苯 为溶剂， 以52%的产率得到TpOs[N(Ph)(BPh2)]Cl2
  参考文献：
  名称：

  10.1002/(sici)1521-3773(19980803)37:13/14<1891::aid-anie1891<3.0.co;2-y

  摘要：

  DOI：

  10.1002/(sici)1521-3773(19980803)37:13/14<1891::aid-anie1891<3.0.co;2-y

文献信息

• Tuning the Properties of the Osmium Nitrido Group in TpOs(N)X₂ by Changing the Ancillary Ligand
  作者：Ahmad Dehestani、Werner Kaminsky、James M. Mayer

  DOI：10.1021/ic0260264

  日期：2003.1.1

  TpOs(N)(OAc)(2) (2) is formed upon reaction of TpOs(N)Cl-2 (1) with excess silver acetate (Tp = hydrotrispyrazolylborate). Treatment of 2 with protic acids HX gives the osmium(VI) complexes TpOs(N)X-2, where X = trifluoroacetate (TFA, 3), trichloroacetate (TCA, 4), tribromoacetate (TBA, 5), bromide (6), oxalate (X2 = O2C2O2, 7), or nitrate (ONO2, 8). Cyclic voltammetry studies of 1-8 show irreversible reductions of Os-VI to Os-V, varying over a range of 0.63 V. Much smaller relative variations are observed in N-15 NMR chemical shifts, v(OsdropN) stretching frequencies, and optical absorbances. Compounds 1-8 all react with PPh3 by nucleophilic attack at the nitride ligand, yielding TpOs(NPPh3)X-2. The reactions are accelerated by more electron withdrawing ligands X. The relative rates correlate with the peak reduction potentials although the effect is small: the rates vary by only 10(2) while the 0.63 V change in E-p,E-c corresponds to a change in equilibrium constant for electron transfer of similar to10(11). Compounds 1-8 also react with triphenylboron, BPh3, with formation of borylanilido complexes TpOs[N(Ph)BPh2]X-2. However, rate constants for reactions with BPh3 to yield Os-IV boryl-amido complexes do not in general correlate with one-electron-reduction potentials. This is likely due to the mechanism of the BPh3 reactions being a two-step process and not simply nucleophilic attack.