New highly stable metallabenzenes via nucleophilic aromatic substitution reaction.
New highly stable metallabenzenes via nucleophilic aromatic substitution reaction.
复制标题
DOI：
10.1002/chem.201003566
复制
发表时间：
2011-04
期刊：
影响因子：
--
通讯作者：
Ran Lin;Hong Zhang;Shunhua Li;Jia-Ni Wang;H. Xia
中科院分区：
文献类型：
--
作者：
Ran Lin;Hong Zhang;Shunhua Li;Jia-Ni Wang;H. Xia
在CH（3）COONa存在下，在空气气氛下，用过量的8-羟基喹啉处理对苯二甲酸[Ru{CHC（PPh（3））CHC（PPh（3））CH}Cl（2）（PPh（3））（2）]Cl（1），得到S（N）Ar产物[（C（9）H（6）NO）Ru{CHC（PPh（3））CHC（PPh（3））C}（C（9）H（6）NO）（PPh（3））]Cl（2）（3）。钌苯3在弱碱或弱酸溶液中稳定。然而，3与NaOH的反应提供了7：1的双烯苯[（C（9）H（6）NO）Ru{CHC（PPh（3））CHCHC}（C（9）H（6）NO）（PPh（3））]Cl（4）和[（C（9）H（6）NO）Ru{CHCHC（PPh（3））C}（C（9）H（6）NO）（PPh（3））]Cl（5）的混合物，推测涉及金属配体的P-C键断裂。配合物3对HCl也有反应活性，导致3以高产率转化为双烯苯[Ru{CHC（PPh（3））CHC（PPh（3））C}Cl（2）（C（9）H（6）NO）（PPh（3））]Cl（6）。热稳定性测试表明，在空气气氛下，顺丁烯二苯4、5和6在固态和溶液中均具有显著的热稳定性。发现钌苯4和5在普通溶剂中是荧光的，并且具有与那些含有大π扩展系统的有机多环化合物相当的光谱行为。
Treatment of the ruthenabenzene [Ru{CHC(PPh(3))CHC(PPh(3))CH}Cl(2)(PPh(3))(2)]Cl (1) with excess 8-hydroxyquinoline in the presence of CH(3)COONa under air atmosphere produced the S(N)Ar product [(C(9) H(6)NO)Ru{CHC(PPh(3))CHC(PPh(3))C}(C(9)H(6)NO)(PPh(3))]Cl(2) (3). Ruthenabenzene 3 could be stable in the solution of weak alkali or weak acid. However, reaction of 3 with NaOH afforded a 7:1 mixture of ruthenabenzenes [(C(9)H(6)NO)Ru{CHC(PPh(3))CHCHC}(C(9)H(6)NO)(PPh(3))]Cl (4) and [(C(9)H(6)NO)Ru{CHCHCHC(PPh(3))C}(C(9)H(6)NO)(PPh(3))]Cl (5), presumably involving a P-C bond cleavage of the metallacycle. Complex 3 was also reactive to HCl, which results in a transformation of 3 to ruthenabenzene [Ru{CHC(PPh(3))CHC(PPh(3))C}Cl(2)(C(9)H(6)NO)(PPh(3))]Cl (6) in high yield. Thermal stability tests showed that ruthenabenzenes 4, 5, and 6 have remarkable thermal stability both in solid state and in solution under air atmosphere. Ruthenabenzenes 4 and 5 were found to be fluorescent in common solvents and have spectral behaviors comparable to those organic multicyclic compounds containing large π-extended systems.