| 1266238-93-0

• CAS: 1266238-93-0
• 化学式: C₂₃H₂₅ClN₃Rh
• 分子量: 481.83
• InChiKey: LZXVMQWSUKJTAE-ONEVTFJLSA-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：

  一氧化碳 、 以 not given 为溶剂， 以99%的产率得到[(C₂N₃(CH₃)(C₆H₅)2)RhCl(CO)2]
  参考文献：
  名称：

  Synthesis and Tunability of Abnormal 1,2,3-Triazolylidene Palladium and Rhodium Complexes

  摘要：

  Palladation of N3-alkylated 1,2,3-triazolium salts with Pd(OAc)(2) afforded a mu(2)-I-2 bridged bimetallic complex [Pd(trz)I-2](2) and monometallic bis(carbene) complexes Pd(trz)(2)I-2 as a mixture of trans and cis isomers (trz = 1,2,3-triazol-5-ylidene). Addition of excess halide or modification of the palladation procedure from direct functionalization to a transmetalation sequence involving a silver intermediate allowed for chemoselective formation of the bis(carbene) complex, while subsequent anion metathesis with NaI produced the monometallic bis(carbene) complexes exclusively. Modification of the wingtip group had little influence on the metalation to palladium or rhodium(I) via transmetalation. According to NMR analysis using delta(C) and (1)J(Rh-C), subtle but noticeable tunability of the metal electronic properties was identified. In addition, phenyl wingtip groups as N-substituents in the triazolylidene ligands were susceptible to cyclopalladation in the presence of NaOAc and are thus not chemically inert.

  DOI：

  10.1021/om101076u
• 作为产物：
  描述：

  3-methyl-1,4-diphenyl-1H-1,2,3-triazol-3-ium iodide 、 chloro(1,5-cyclooctadiene)rhodium(I) dimer 在 Ag₂O 作用下， 以 二氯甲烷 为溶剂， 以55%的产率得到
  参考文献：
  名称：

  Synthesis and Tunability of Abnormal 1,2,3-Triazolylidene Palladium and Rhodium Complexes

  摘要：

  Palladation of N3-alkylated 1,2,3-triazolium salts with Pd(OAc)(2) afforded a mu(2)-I-2 bridged bimetallic complex [Pd(trz)I-2](2) and monometallic bis(carbene) complexes Pd(trz)(2)I-2 as a mixture of trans and cis isomers (trz = 1,2,3-triazol-5-ylidene). Addition of excess halide or modification of the palladation procedure from direct functionalization to a transmetalation sequence involving a silver intermediate allowed for chemoselective formation of the bis(carbene) complex, while subsequent anion metathesis with NaI produced the monometallic bis(carbene) complexes exclusively. Modification of the wingtip group had little influence on the metalation to palladium or rhodium(I) via transmetalation. According to NMR analysis using delta(C) and (1)J(Rh-C), subtle but noticeable tunability of the metal electronic properties was identified. In addition, phenyl wingtip groups as N-substituents in the triazolylidene ligands were susceptible to cyclopalladation in the presence of NaOAc and are thus not chemically inert.

  DOI：

  10.1021/om101076u

文献信息

• Regioselective Electrophilic C–H Bond Activation in Triazolylidene Metal Complexes Containing a N-Bound Phenyl Substituent
  作者：Kate F. Donnelly、Ralte Lalrempuia、Helge Müller-Bunz、Martin Albrecht

  DOI：10.1021/om300983m

  日期：2012.12.10

  Transmetalation of a 1,4-diphenyl-substituted 1,2,3-triazolylidene silver complex with an electrophilic metal center, e.g., RuII, IrIII, or RhIII, induces spontaneous and chemoselective cyclometalation involving C–H bond activation of the N-bound phenyl group exclusively. Less electrophilic metals such as IrI, RhI, and PtII yield a monodentate triazolylidene complex, while cyclometalation with borderline

  1,4-二苯基取代的1,2,3-三唑基亚银与亲电子金属中心（例如Ru II，Ir III或Rh III）的金属转移会诱导自发和化学选择性的环金属化，涉及环的C–H键活化仅与N结合的苯基。较少的亲电金属（例如Ir I，Rh I和Pt II）会生成单齿三唑基亚烷基络合物，而在临界情况下（Pd II）进行环金属化或C结合苯环的活化需要乙酸盐作为促进剂。