[1,1,1,-tris((dimethylphosphino)methyl)ethane]RhMe(OSO2CF3)2 | 181310-03-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: [1,1,1,-tris((dimethylphosphino)methyl)ethane]RhMe(OSO2CF3)2
• 英文别名: carbanide;[3-dimethylphosphanyl-2-(dimethylphosphanylmethyl)-2-methylpropyl]-dimethylphosphane;rhodium(3+);trifluoromethanesulfonate
• CAS: 181310-03-2
• 化学式: C₁₄H₃₀F₆O₆P₃RhS₂
• 分子量: 668.338
• InChiKey: WRTKGIQVKHVTNI-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  4.77
• 重原子数：
  32
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  131
• 氢给体数：
  0
• 氢受体数：
  13

反应信息

• 作为产物：
  描述：

  [1,1,1,-tris((dimethylphosphino)methyl)ethane]RhMe3 、 三氟甲磺酸 以 乙醚 、 二氯甲烷 为溶剂， 以91%的产率得到[1,1,1,-tris((dimethylphosphino)methyl)ethane]RhMe(OSO2CF3)2
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1021/om9601099