trans-Rh(OC6H4NO2-p)(CO)(PPh3)2 | 215788-21-9

• 英文名称: trans-Rh(OC6H4NO2-p)(CO)(PPh3)2
• CAS: 215788-21-9
• 化学式: C₄₃H₃₄NO₄P₂Rh
• 分子量: 793.6
• InChiKey: YWEVTNKAWMIWER-UHFFFAOYSA-M

反应信息

• 作为产物：
  描述：

  以 甲苯 、 苯 为溶剂， 生成 trans-Rh(OC6H4NO2-p)(CO)(PPh3)2
  参考文献：
  名称：

  Preparation, structure and properties of triphenylphosphine rhodium aryloxides

  摘要：

  The reaction of Wilkinson's catalyst with NaOAr in toluene cleanly affords the corresponding aryloxide complexes Rh(PPh3)(3)OAr (1), In solution, 1. exists in equilibrium with PPh3 and the corresponding Rh(PPh3)(2)(pi-ArO) (2). The addition of HOAr shifts the equilibrium completely toward the corresponding adducts 2.2HOAr, due to hydrogen bonding between the oxygen atom of the pi-coordinated OAr ligand and two molecules of HOAr. Heating of 1a-d in toluene at 60-80 degrees C leads to the elimination ui HOAr with concomitant cyclometallation uf a phenyl ring of one PPh3 ligand, affording mixtures of 1, 2.2HOAr, a cyclometallated Rh complex and PPh3. At room temperature, a reverse reaction slowly occurs to give equilibrium mixtures of 1, 2 and PPh3. Complexes 1 readily react with water, CO and H-2, affording Rh-2(PPh3)(4)( mu-OH)(2),Rh(PPh3)(2)(CO)OAr (3) and HRh(PPh3)(3), respectively. The latter complex was also obtained when complexes 1 were treated with methanol. The structures of the phenoxide complexes 1 and 2.2PhOH and of p-nitrophenoxide complex 3 were established by X-ray diffraction. (C) 1998 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0020-1693(98)00171-6

文献信息

• Solid–gas carbonylation of aryloxide rhodium(I) complexes: stepwise reaction forming Vaska-type complexes
  作者：Kohtaro Osakada、Hidetake Ishii

  DOI：10.1016/j.ica.2004.02.030

  日期：2004.7

  Aryloxide rhodium(I) complexes Rh(OAr)(PPh3)(3) (1a: Ar=C6Cl5, 1b: Ar=C6F5, 1c: Ar= C6H4-NO2-4) react with CO in toluene solutions to produce Vaska-type complexes trans-Rh(OAr)(CO)(PPh3)(2) (2a: Ar=C6Cl5, 2b: Ar=C6F5, 2c: Ar=C6H4-NO2-4). Carbonylation of a similar complex with PMe3 ligands, Rh(OC6H4-NO2-4)(PMe3)(3) (3c), also forms trans-Rh(OC6H4-NO2-4)(CO)(PMe3)(2) (4c). Molecular structures of the complexes are determined by X-ray crystallography and NMR spectroscopy. Complex I a reacts with CO in the absence of solvent to produce a mixture of 2a and complex A, the latter of which shows the IR and C-13H-1} signals due to the carbonyl ligand at different positions from those of 2a. Addition of Et2O to the above mixture turns it into analytically pure 2a. Carbonylation of 1b and 1c under the solvent-free conditions produces complexes B and C as the respective products of the solid-gas reaction. Recrystallization of It and C turns them into 2b and 2c, respectively. Complex 3c also reacts with CO in the solid state to form a mixture of 4c and complex D, although the latter complex is converted slowly into 4c even in the solid state. (C) 2004 Elsevier B.V. All rights reserved.