Preparation, structure and properties of triphenylphosphine rhodium aryloxides
详细信息 查看全文
- 作者：Kuznetsov ; Vladimir F. ; Yap ; Glenn P.A. ; Bensimon ; Corinne ; Alper ; Howard
- 关键词：Crystal structures ; Rhodium complexes ; Aryloxide complexes
- 刊名：Inorganica Chimica Acta
- 出版年：1998
- 出版时间：October 15, 1998
- 年：1998
- 卷：280
- 期：1-2
- 页码：172-182
- 全文大小：799 K
文摘
The reaction of Wilkinson's catalyst with NaOAr in toluene cleanly affords the corresponding aryloxide complexes Rh(PPh3)3OAr (1). In solution, 1 exists in equilibrium with PPh3 and the corresponding Rh(PPh3)2 (π-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 π-coordinated OAr ligand and two molecules of HOAr. Heating of 1a-d in toluene at 60-80°C leads to the elimination of HOAr with concomitant cyclometallation of 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 H2, affording Rh2(PPh3)4(μ-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.