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.