[(η(5)-C5Me5)(PMe3)Ir(S-p-tolyl)2] | 173203-28-6

• 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: [(η(5)-C5Me5)(PMe3)Ir(S-p-tolyl)2]
• 英文别名: Cp*Ir(PMe3)(S-p-tolyl)2；iridium(3+);4-methylbenzenethiolate;1,2,3,4,5-pentamethylcyclopenta-1,3-diene;trimethylphosphane
• CAS: 173203-28-6
• 化学式: C₂₇H₃₈IrPS₂
• 分子量: 649.924
• InChiKey: NCNNTMDXQYSBHK-UHFFFAOYSA-L

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

• 作为产物：
  描述：

  [(η(5)-C5Me5)(PMe3)Ir(CH2C(O)CH3)(S-p-tolyl)] 、 potassium p-tolylthiolate 以 not given 为溶剂， 生成 [(η(5)-C5Me5)(PMe3)Ir(S-p-tolyl)2]
  参考文献：
  名称：

  CH bond activation in functionalized organic compounds with Cp∗ (PMe3)IrMe(OTf): generation, structural characterization and metal-based rearrangement of the acetone activation product Cp∗ (PMe3)Ir(η3-CH2C(OH)CH2)+OTf−

  摘要：

  The iridium complex Cp*(PMe(3))Ir(Me)OTf (1) (Cp* = eta(5)-C-5(CH3)(5), OTf = OSO2CF3) reacts cleanly with acetone at room temperature. This reaction results in overall double C-H activation, generating the cationic eta(3)-hydroxyallyl complex Cp*(PMe(3))Ir(eta(3)-CH2C(OH)CH2)(+)OTf(-) (2), Complex 2 was characterized by X-ray diffraction and found to contain a hydrogen-bonded triflate anion. The ultimate product formed on reaction with acetone is strongly dependent upon the nature of the counterion present. Replacement of the triflate ion in 2 with other anions leads to the metallacyclobutanone Cp*(PMe(3))Ir(eta(2)-CH2COCH2), the eta(1)-enolate Cp*(PMe(3))Ir(CH2COCH3)S(p-tolyl) and the free cation salt Cp*(PMe(3))Ir(eta(3)-CH2C(OH)CH2)(+) B(3,5-C6H3(CF3)(2))(4)(-).

  DOI：

  10.1016/0022-328x(95)05614-u

文献信息

• Synthesis and Chemistry of the Aryliridium(III) Fluorides Cp'Ir(PMe3)(Aryl)F: High Reactivity due to Surprisingly Easy Ir-F Ionization
  作者：John E. Veltheer、Peter Burger、Robert G. Bergman

  DOI：10.1021/ja00155a012

  日期：1995.12

  This paper reports the synthesis and chemistry of the unusual late metal fluoride complexes, Cp'Ir-(PMe(3))(Aryl)F [Cp' = Cp* (C(5)Me(5)), Aryl = Ph (1a); Cp' = Cp*, Aryl = p-tolyl (1b); Cp' = Cp(Et) (C(5)Me(4)Et), Aryl = Ph(1c)]. The solid-state structure of Ic has been determined: crystals of 1c are monoclinic, space group P2(1)/c, with a = 9.235(2) Angstrom, b = 12.667(2) Angstrom, c = 17.129(3) Angstrom, beta 104.547(16)degrees, and Z = 4; R = 3.98%, wR = 4.65% for 2859 data for F-2 > 3 sigma(F-2). These complexes exhibit reactivity that is substantially different from that of related Cl, Pr, and I species because of the greater propensity of fluoride ion to dissociate from the Ir center, even in nonpolar solvents. For example, in solution at room temperature, fluoride is slowly displaced from complexes 1 by Lewis bases such as pyridines and phosphines (L); the resulting salts [Cp'Ir(PMe(3))(Aryl)(L)]F (2) exist in equilibrium with the covalent starting materials. This equilibrium Lies well to the left for pyridines and phosphines under anhydrous conditions, but both the rate of establishment and the magnitude of K-eq are increased dramatically by the addition of H2O. In aqueous THF the aquo species [Cp*Ir(PMe(3))(Ph)(OH2)]F . xH(2)O (2e) is formed much more rapidly than the [Cp'Ir(PMe(3))(Aryl)(L)]F salts. This, and the rapid further reactivity of 2e, enables the aquo species to serve as an intermediate in the water-catalyzed substitution of fluoride by L. Treatment of la with mixtures of water and other entering ligands and monitoring these reactions over time reveals that the kinetic affinity of these ligands for the Ir center is exactly the reverse of their thermodynamic affinity: kinetically, H2O > pyridines > phosphines; thermodynamically, phosphines > pyridines > H2O. Addition of BPh(3) to [Cp'Ir(PMe(3))(Aryl)(L)]F (2) in nonaqueous media leads to irreversible formation of the berate complexes, [Cp'Ir(PMe(3))(Aryl)(L)]BPh(3)F. The lability of the fluoride Ligand in complexes 1 is also demonstrated by mixing Cp*Ir(PMe(3))(Ph)F with Cp*Ir(PMe(3))(p-tolyl)X IX Cl, Pr, OTf, OPh] in C6D6, which leads to solutions containing four species identifiable as the two starting materials and the two exchange products Cp*Ir(PMe(3))Ph)X and Cp*Ir(PMe(3))p-tolyl)F. Organic halides participate in exchange as well; reaction of la with PhCH(2)Br, Me(3)SiCl, MeCOCl, and even CH2Cl2 results in complete replacement of fluoride by bromide or chloride in la. The labile fluoride ion also leads to other novel reactivity. For example, addition of dimethyl acetylenedicarboxylate to complexes 1 gives iridacyclopentadiene complexes (5) and reaction of la and Ic with (l-trimethylsilyl)imidazole provides Cp'Ir(PMe(3))(Ph)(imidazolate) complexes (7) and Me(3)SiF. Treatment of 1 with silanes HSiMe(2)R [R = Ph, Me] leads to the formation of Cp'Ir(PMe(3))(R)(SiMe(2)F) complexes(8); excess HS-p-tolyl reacts with either 1a or 1b to provide Cp*Ir(PMe(3))(S-p-tolyl)(2) (10).