Transition Metal Complexes of Diazenes, XXXVIII [1] Activation of Aromatic C-Cl Bonds in the Oxidative Addition of ortho-Chlorophenyldiazenes to Chlorotris(triphenylphosphine)rhodium
作者:Uwe R. Aulwurm、Falk Knoch、Horst Kisch
DOI:10.1515/znb-1996-1103
日期:1996.11.1
6-trichloroazobenzene affords cyclometalated complexes (1) via loss of one phosphine ligand and oxidative addition of the ortho -C-Cl bond. X-ray structural analysis indicates a trans-position of the two triphenylphosphine ligands. The reaction proceeds only in polar solvents like alcohols or dimethyl sulfoxide but not in toluene. In the presence of air or oxygen a hydrido complex was formed as a by-product.
回流 RhCl(PPh3)3 和 2-氯-、2,4-二氯-或 2,4,6-三氯偶氮苯的微酸性 n-BuOH 溶液,通过失去一个膦配体和氧化加成得到环金属化配合物 (1)邻-C-Cl键。X 射线结构分析表明两个三苯基膦配体的转位。该反应仅在极性溶剂(如醇或二甲亚砜)中进行,而不能在甲苯中进行。在空气或氧气存在下,氢化物络合物作为副产物形成。