| 191415-57-3

• CAS: 191415-57-3
• 化学式: C₃₀H₅₈ClIrO₂P₂
• 分子量: 740.41
• InChiKey: MQNSXRKSVBCWBQ-UHFFFAOYSA-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：

  、 氘 以 甲苯 为溶剂， 以80%的产率得到chloro[dicyclohexyl(methoxyethyl)phosphine-P][dicyclohexyl(methoxyethylyl)phosphine-P,O]-cis-dideuteridoiridium(III)
  参考文献：
  名称：

  Comparative Studies on Ether−Phosphine-Assisted Exchange Processes in the Rhodium(III) and Iridium(III) Complexes ClMH₂(P⌒O)(P∼O)

  摘要：

  The rhodium and iridium complexes ClRhH2(P asymptotic to O)(P similar to O) (2a,b) and ClIrH2(P asymptotic to O)(P similar to O) (3a) (P asymptotic to O = eta(2)(P,O) coordination, P similar to O = eta(1)(P) coordination of Cy2PCH2CH2OCH3 (a) and Cy2PCH2C4H7O (b); C4H7O = tetrahydrofuranyl) were subjected to dynamic NMR studies. They exhibit a fast fluxional behavior both of the two ether oxygen donors and of the two cis hydrides at room temperature. The exchange of the hydrides is assisted by the fact that one of the ether moieties simulates an external solvent. The complexes 2a,b show the same behavior as is suggested for the coordinatively unsaturated species ClRhH2(PPh3)(2), which is generally postulated to be an active intermediate in the catalytic hydrogenation of olefins. In the course of the formation of 3a from its ortho-metalated precursor ClIrH(POCH2)(P asymptotic to O) (4a; POCH2 = eta(2)(P,CH2) coordination of Cy2PCH2CH2OCH2) and dihydrogen, one C-H bond of the methoxy group and an additional Ir-H bond were formed. This was confirmed by the corresponding reaction of 4a with D-2 to give the analogous dideuterium complex 3a'. The opposite behavior was observed when 4a was treated with DCl: one C-D and one Ir-Cl bond were formed in the complex Cl2IrH(P asymptotic to O)(P similar to O)(5a; one Cy2PCH2CH2OCH2D ligand) while the hydride remained at the metal. The Rh-103 chemical shift has been determined for compound 2b.

  DOI：

  10.1021/om970105j

文献信息

• Reactivity and chemical exchange processes of bis(ether-phosphine) iridium(III) complexes
  作者：Ekkerhard Lindner、Karlheinz Gierling、Riad Fawzi、Manfred Steinmann

  DOI：10.1016/s0020-1693(97)05769-1

  日期：1998.3

  The orthometalated indium(III) complex CIIrH(POCH2)(PO) (POCH2 = eta(2)(P, OCH2) coordination of Cy2PCH2CH2OCH2, PO = eta(2)(P, O) coordination of Cy2PCH2CH2OCH3) (1) reacts with CS2, HCl, and H-2 under re-formation of the methoxy group to give CIIr(eta(2)-CS2)(P similar to O)(2) (3) (P similar to O =eta 1(P) coordination of Cy2PCH2CH2OCH3), trans-(PO)(P similar to O)Ir(H)Cl-2 (4a) and CIIrH2(PO)(P similar to O) (5), respectively. Upon the reaction of 1 with CO the orthometalation is maintained to yield the carbonyl adduct CIIrH(CO)(POCH2)(P similar to O) (2). Compounds 4a and 5 represent potentially unsaturated speices weakly protected by the ether moiety which acts as an intramolecular solvent. The chelated five-membered ring in 4a, cis-(PO)(P similar to O)Ir(H)Cl-2 (4b) and 5 can easily be cleaved by carbon monoxide, pyridine and CS2 whereby the complexes Cl2IrH(CO)(P similar to O)(2) (7), CIIrH2(C5H5N)(P similar to O)(2) (10), CIIrH2(CO)(P similar to O)(2) (11) and the dithioformato complex cis-(P similar to O)(2)Ir(H)Cl(S2CH) (13a) are formed. In toluene 13a isomerizes to give the trans-product 13b. Comparative NMR studies on the fluxional behavior of the ether phosphine ligands of the five monochelated complexes 4a, b, 5, IrH3(P similar to O)(2) (6) and Cl3Ir(PO)(P similar to O) (9a) were performed to determine the dependence of the exchange rates on the strength of the indium-(ether) oxygen bond. Complex 9b, the phenyl congener of 9a, crystallizes in the orthorhombic space group Pna2(1) with Z = 4. The cell dimension are a = 1695.2(3), b = 1093.4(2), c = 1621.5(9) pm, R-1 = 0.018 and wR(2) = 0.042. (C) 1998 Elsevier Science S. A.