trimethyl(1,4,7-trimethyl-1,4,7-triazacyclononane)rhodium(III) | 140149-52-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪烷类
• 英文名称: trimethyl(1,4,7-trimethyl-1,4,7-triazacyclononane)rhodium(III)
• 英文别名: (1,4,7-trimethyl-1,4,7-triazacyclononane)RhMe3；Carbanide;rhodium(3+);1,4,7-trimethyl-1,4,7-triazonane
• CAS: 140149-52-6
• 化学式: C₁₂H₃₀N₃Rh
• 分子量: 319.296
• InChiKey: PIXRMZRPQAFJQG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.14
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  9.7
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  trimethyl(1,4,7-trimethyl-1,4,7-triazacyclononane)rhodium(III) 以 四氢呋喃 、 乙醚 、 二氯甲烷 为溶剂， 生成 (1,4,7-trimethyl-1,4,7-triazacyclononane)RhMe2Br
  参考文献：
  名称：

  （1,4,7-三甲基-1,4,7-三氮杂环壬烷）RhMe 3，其某些Rh-C酸裂解衍生物和（1,4,7-三氢己基-1,4,7-三氮杂环壬烷的制备Rhme 3

  摘要：

  已经合成并表征了一系列Cn配位的有机铑络合物CnRhMe 3- n X n和Nh CnRhMe 3（n = 1-3; Cn = 1,4,7-三甲基-1,4,7-三氮杂环壬烷; Nh Cn = 1,4,7- trineohexyl-1,4,7-三氮杂; X =氯- ，溴- ，光学传递函数-，BF 4 - ）。CnRhMe 3（1）和Nh CnRhMe 3的X射线衍射数据显示了Cn的预期面部配位。Rh-N长度显示出来自强场甲基的较大反式影响。在1铑甲基的1 H NMR化学位移显示出与Rh上吸电子取代基的取代度（n）良好的相关性。CnRhMe 3- Ñ X Ñ（Ñ = 1，2）具有良好定义的溶剂配位性能，当X =光学传递函数-和BF 4 - 。阴离子的此CNRH系统的配位能力如下趋势BF 4 - <光学传递函数- «溴- <氯- 。溶剂的这些复合物中的相对配位能力是CH 2氯2 «甲醇

  DOI：

  10.1021/om9506577
• 作为产物：
  描述：

  trichloro(N,N',N''-trimethyl-1,4,7-trazacyclononane)rhodium(III) 、 甲基锂 在 H₂O 作用下， 以 四氢呋喃 为溶剂， 以85%的产率得到trimethyl(1,4,7-trimethyl-1,4,7-triazacyclononane)rhodium(III)
  参考文献：
  名称：

  （1,4,7-三甲基-1,4,7-三氮杂环壬烷）RhMe 3，其某些Rh-C酸裂解衍生物和（1,4,7-三氢己基-1,4,7-三氮杂环壬烷的制备Rhme 3

  摘要：

  已经合成并表征了一系列Cn配位的有机铑络合物CnRhMe 3- n X n和Nh CnRhMe 3（n = 1-3; Cn = 1,4,7-三甲基-1,4,7-三氮杂环壬烷; Nh Cn = 1,4,7- trineohexyl-1,4,7-三氮杂; X =氯- ，溴- ，光学传递函数-，BF 4 - ）。CnRhMe 3（1）和Nh CnRhMe 3的X射线衍射数据显示了Cn的预期面部配位。Rh-N长度显示出来自强场甲基的较大反式影响。在1铑甲基的1 H NMR化学位移显示出与Rh上吸电子取代基的取代度（n）良好的相关性。CnRhMe 3- Ñ X Ñ（Ñ = 1，2）具有良好定义的溶剂配位性能，当X =光学传递函数-和BF 4 - 。阴离子的此CNRH系统的配位能力如下趋势BF 4 - <光学传递函数- «溴- <氯- 。溶剂的这些复合物中的相对配位能力是CH 2氯2 «甲醇

  DOI：

  10.1021/om9506577

文献信息

• An organometallic Rh^IIIcomplex with a distorted octahedral structure: (acetonitrile-κ<i>N</i>)dimethyl(1,4,7-trimethyl-1,4,7-triazacyclononane-κ³<i>N</i>,<i>N</i>′,<i>N</i>′′)rhodium(III) tetraphenylborate
  作者：Erik Fooladi、Bjørn Dalhus、Christian Rømming、Mats Tilset

  DOI：10.1107/s0108270102019182

  日期：2002.12.15

  In the title compound, [Rh(CH(3))(2)(C(2)H(3)N)(C(9)H(21)N(3))](C(24)H(20)B), the geometry around the Rh(III) centre is distorted octahedral, with elongated Rh-N bonds trans to the metal-bonded methyl groups. The metal-containing cations are located in channels formed by an anionic supramolecular mesh, in which aromatic pi-pi interactions between anionic [B(Ph)(4)](-) units play a major role.

  在标题化合物中，[Rh（CH（3））（2）（C（2）H（3）N）（C（9）H（21）N（3））]（C（24）H（20 ）B），Rh（III）中心周围的几何形状是扭曲的八面体，带有延伸到金属键合的甲基的细长Rh-N键。含金属的阳离子位于由阴离子超分子网形成的通道中，其中阴离子[B（Ph）（4）]（-）单元之间的芳香pi-pi相互作用起主要作用。
• Fooladi, Erik; Tilset, Mats, Inorganic Chemistry, 1997, vol. 36, # 26, p. 6021 - 6027
  作者：Fooladi, Erik、Tilset, Mats

  DOI：——

  日期：——
• XPS Investigations of (1,4,7-trimethyl-1,4,7-triazacyclononane)RhMe₃ and [1,1,1-tris((dimethylphosphino)methyl)ethane]RhMe₃ and Their Rh−C Cleavage Derivatives. Comparison of Hard- and Soft-Ligated Rhodium Organometallics
  作者：Lin Wang、John R. Sowa,、Chunming Wang、Roy S. Lu、Paul G. Gassman、Thomas C. Flood

  DOI：10.1021/om9601099

  日期：1996.10.1

  The new molecules P(3)RhMe(3-n)(OTf)(n) are reported (n = 0-2; P-3 = MeC(CH(2)PMe(2))(3); OTf = OS(O)(2)CF3). The known fac-(Me(3)P)(3)RhMe(3) was converted to mer-(Me(3)P)(3)RhMe(3-n)Cl(n). (n = 1, 2) by cleavage with HCl in ether. X-ray photoelectron spectra (XPS) of these were recorded, and all except the P(3)RhMe(3-n)Cl(n) series afforded clean spectra. XPS were also obtained for the known CnRhMe(3-n)X(n) (n = 0-2; X = Cl, Br, OTf; Cn = 1,4,7-trimethyl-1,4,7-triazacyclononane), CnRhX(3) (X = Cl, Br), CnRhMe(OH)(OTf), and [CnRhMe(2)(CO)]OTf. An X-ray crystal structure of P(3)RhMe(3) is reported, and the geometry at the metal is compared among P(3)RhMe(3), (Me(3)P)(3)RhMe(3), and CnRhMe(3). Core binding energies (BEs) for the series L(3)RhMe(3-n)X(n) (L(3) = Cn, P-3) change linearly with n for a given L(3) and X. For CnRhMe(3-n)X(n), replacement of methyl by chloride or bromide gives similar Delta BE values (similar to 0.7 eV), while triflate-for-methyl substitution gives a much larger Delta BE (1.2 eV). Triflate-for-methyl substitution in P(3)RhMe(3-n)(OTf)(n), however, causes a Delta BE of only 0.8 eV. Thus, the Rh(3d(5/2)) core binding energies in these complexes change less in triflate-for-methyl substitutions when the P-3 ancillary ligand is present than in the presence of Cn; apparently P-3 compensates for changes in electron density at the rhodium center more effectively than does Cn, presumably as a result of the greater polarizability of phosphorus (softer) compared to nitrogen (harder). The XPS trends for these series effectively mean that P-3 makes Rh-III a softer metal and Cn makes Rh-III a harder metal.