tris(2,6-dimethylphenyl)rhodium(III) | 138866-52-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: tris(2,6-dimethylphenyl)rhodium(III)
• CAS: 138866-52-1
• 化学式: C₂₄H₂₇Rh
• 分子量: 418.384
• InChiKey: KYFQHXMEZXVPGK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.43
• 重原子数：
  25.0
• 可旋转键数：
  3.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  2,6-二甲基苯基溴化镁 、 RhCl3(tetrahydrothiophen)3 以 四氢呋喃 、 乙醚 为溶剂， 以35%的产率得到tris(2,6-dimethylphenyl)rhodium(III)
  参考文献：
  名称：

  Aryl compounds of rhodium: syntheses and X-ray crystal structures

  摘要：

  The interactions of fac-RhCl3(tht)3, tht = tetrahydrothiophene, with aryl-lithium or -magnesium bromide reagents, aryl = 2,4,6-R3C6H2 (R = Me or Pr(i)), 2,6-Me2C6H3, or 2-MeC6H4, and also Mg(PhCH2)Br, have been studied. With Li(2,4,6-Pr(i)3C6H2)(Et2O) only the unique, square, paramagnetic rhodium(II) compound trans-Rh(2,4,6-Pr(i)3C6H2)2(tht)2 is obtained. This reacts with CO reversibly to give labile carbonyl species and with Bu(t)NC to give the rhodium(I) sigma-bonded iminoacyl Rh(CNBu(t))3(2,4,6-Pr(i)3C6H2C = NBu(t)). A similar mesityl (mes) compound is obtained from Rh(mes)3 and Bu(t)NC. Homoleptic rhodium(III) aryls Rh(aryl)3 have been obtained for aryl = 2,6-Me2C6H3 and 2,4,6-Me3C6H2. The mesityl reacts with CO to give a carbonyl species that has a bridged acyl and a bridge in which a mesityl group sigma-bonded to one Rh atom is bound eta-6 to the other. It also reacts with PMe2Ph to give Rh(mes)(PMe2Ph)3. The interaction of RhCl3(tht)3 with Mg(PhCH2)Br gives only the unsymmetric bridged species (tht)(PhCH2)2Rh(mu-Cl)3Rh(CH2Ph)(tht)2. The crystal structures of six compounds have been determined: trans-Rh(2,4,6-Pr(i)3C6H2)2(tht)2 is square with a two-fold axis of symmetry perpendicular to the molecular plane [Rh-C and Rh-S 2.11(1) and 2.291(5) angstrom]. The compounds Rh(CNBu(t))3(sigma-RC = NBu(t)), (R = 2,4,6-Me3C6H2 or 2,4,6-Pr(i)3C6H2) have similar structures in which the rhodium(I) centres are square [Rh-C (isocyanide) and Rh-C (imino) 1.88-1.94(2) and 2.08 and 2.06(2) angstrom]. The compound Rh2(2,4,6-Me3C6H2CO)(2,4,6-Me3C6H2(CO)3 contains two rhodium centres with quite different co-ordination: Rh(1) is square with bonds to two carbonyls [Rh-C 1.81(1) and 1.90(1) angstrom], an aryl [Rh-C 2.07(1) angstrom] and an oxygen from the aroyl ligand [Rh-O 2.08(1) angstrom]; Rh(2) is trigonal bipyramidal with the aryl sigma-bonded to Rh(1) now eta-6 bonded over two equatorial [Rh-C 2.33(1) and 2.34(1) angstrom] and one axial [Rh-C 2.44(1) angstrom] sites, the remaining axial and equatorial sites being occupied by the aroyl carbon [Rh-C 1.94(1) angstrom] and a carbonyl group [Rh-C 1.84(1) angstrom]. The compound Rh(2,4,6-Me3C6H2)(PMe2Ph)3 has square rhodium(I) geometry [Rh-C 2.09(1) and Rh-P 2.304(4) angstrom (trans to the aryl) and 2.276(4) and 2.287(4) angstrom trans to each other]. The dimer Rh2(PhCH2)3Cl3(tht)3 has a confacial bioctahedral structure with Rh-Cl, Rh-C and Rh-S distances showing considerable variations due to the differing trans influences of the three ligand types.

  DOI：

  10.1039/dt9910002821