| 131703-26-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• CAS: 131703-26-9
• 化学式: C₄₈H₅₂NP₃RuSi₂
• 分子量: 893.11
• InChiKey: WLOIBJCXNFBDJW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.68
• 重原子数：
  55.0
• 可旋转键数：
  8.0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  3.24
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为产物：
  描述：

  在 H₂ 作用下， 以 甲苯 为溶剂， 以85%的产率得到
  参考文献：
  名称：

  Synthesis and reactivity of ruthenium amide-phosphine complexes. Facile conversion of a ruthenium amide to a ruthenium amine via dihydrogen activation and orthometalation. X-ray structure of RuCl(C6H4PPh2)[NH(SiMe2CH2PPh2)2]

  摘要：

  The reaction of LiN(SiMe2CH2PPh2)2 with RuCl2(PPh3)3 leads to the formation of the ruthenium amide complex RuCl(PPh3)[N(SiMe2CH2PPh2)2]. This complex reacts with H2 to form two isomeric amine-hydride derivatives of the formula RuCl(PPh3)H[NH(SiMe2CH2PPh2)2]. Reaction of RuCl(PPh3)[N-(SiMe2CH2PPh2)2] with MeLi, Me3SiCH2Li, or H2C = CHCH2MgCl does not lead to the expected hydrocarbyl derivative; rather, ortho metalation occurs to generate Ru(C6H4PPh2)[N(SiMe2CH2PPh2)2]. Attempts to displace the PPh3 ligand of RuCl(PPh3)[N(SiMe2CH2PPh2)2] with PEt3 lead to the formation of RuCl(C6H4PPh2)[NH(SiMe2PPh2)2], having an amine ligand and the ortho-metalated phenyl group. The complex RuCl(C6H4PPh2)[NH(SiMe2CH2PPh2)2] crystallizes in space group P2(1)/n with a = 9.8385 (5) angstrom, b = 29.561 (1) angstrom, c = 20.8665 (9) angstrom, beta = 101.683 (4)-degrees, V = 5942.2 (5) angstrom3, and Z = 4. Transformation of an amide linkage to an amide via H2 activation or ortho metalation is apparently driven by the formation of an intramolecular hydrogen bond between the amine hydrogen and the coordinated chloride; the N-H...Cl distance is 2.76 (6) angstrom, which is shorter than the expected van der Waals separation of 3.0 angstrom.

  DOI：

  10.1021/om00048a025

文献信息

• Amido/phosphine pincer hydrides of ruthenium
  作者：Lori A. Watson、Joseph N. Coalter III、Oleg Ozerov、Maren Pink、John C. Huffman、Kenneth G. Caulton

  DOI：10.1039/b206202j

  日期：2003.1.20

  The chemistry of the ligand (R2PCH2SiMe2)2N− (R=cyclohexyl and tBu), “PNP-R”, on ruthenium is developed, including RuH(PNP-Cy)(PPh3) and (HPNP-R)RuH3Cl. The latter contains a protonated nitrogen (i.e., amine as a donor to Ru) and one H2 ligand (X-ray structure for R=tBu). This compound can be dehydrohalogenated to give (PNP-Cy)RuH3, which undergoes H/D exchange of D2 into its cyclohexyl rings, and

  配位体的化学性质（R 2 PCH 2森达2）2 ñ - （R =环己基和吨丁基），“PNP-R”，钌被显影，包括期RuH（PNP-CY）（PPH 3）和（HPNP -R）RuH 3 Cl。后者包含质子化的氮（即，胺作为Ru的供体）和一个H 2配体（R = t Bu的X射线结构）。该化合物可以脱卤化氢得到（PNP-Cy）RuH 3，其经过D 2的H / D交换进入其环己基环，并且本身被过量的H 2 C脱氢CHR得到[Cy 2 PCH 2 SiMe 2 NSiMe 2 CH 2 PCy（C 6 H 8）] Ru，该Ru包含与Ru结合的三脱氢环己基环π-烯丙基。（PNP-Cy）RuH 3与二氢呋喃反应，得到杂原子稳定的卡宾配合物（PNP-Cy）RuH [ CO（CH 2）3 ]。