Catalytic carbon-carbon bond activation and functionalization by nickel complexes
Catalytic carbon-carbon bond activation and functionalization by nickel complexes
复制标题
DOI：
10.1021/om990387i
复制
发表时间：
1999-09-27
期刊：
影响因子：
2.8
通讯作者：
Jones, WD
中科院分区：
文献类型：
--
作者：
Edelbach, BL;Lachicotte, RJ;Jones, WD
合成了炔镍配合物（dippe）Ni（PhC=CPh），1，（dippe）Ni（MeC=CMe），2，（dippe）Ni（MeO 2CC = CCO 2 Me），3，（dippe）Ni（CH 3 OCH 2C = CCH 2 OCH 3），4和（dippe）Ni（CF 3C = CCF 3），5（dippe =双（二异丙基膦基）乙烷），并通过H-1，P-31和C-13{H-1} NMR谱进行了表征。配合物1，2和3的特征在于通过X-射线晶体学。配合物1或2在过量联亚苯基和过量炔存在下的热分解（120 ℃）导致非常缓慢地催化形成相应的9，10-二取代菲。然而，向反应混合物中添加类似于6摩尔%的0 -2（基于金属络合物）导致在较低温度（类似于70-80 ° C）下催化的加速。过量联苯和过量炔的配合物3或4的热分解导致炔环三聚产物作为反应中形成的主要有机物种。芴酮是通过加热（dippe）Ni（CO）（2）、联苯和CO催化生成的。2，6-二甲苯基异氰化物催化插入联苯的应变C-C键也可以通过加热（dippe）Ni（2，6-二甲苯基异氰化物）（2）、过量的联苯和2，6-二甲苯基异氰化物实现。提出了这些反应的机理方案。
The nickel alkyne complexes (dippe)Ni(PhC=CPh), 1, (dippe)Ni(MeC=CMe), 2, (dippe)Ni(MeO2CC=CCO2Me), 3, (dippe)Ni(CH3OCH2C=CCH2OCH3), 4, and (dippe)Ni(CF3C=CCF3), 5, were synthesized (dippe = bis(diisopropylphosphino)ethane) and characterized by H-1, P-31, and C-13{H-1} NMR spectroscopy. Complexes 1, 2, and 3 were characterized by X-ray crystallography. The thermolysis of complex 1 or 2 (120 degrees C) in the presence of excess biphenylene and excess alkyne results in very slow catalytic formation of the corresponding 9,10-disubstituted phenanthrene. However, addition of similar to 6 mol % O-2 (based on the metal complex) to the reaction mixture results in an acceleration in catalysis at lower temperatures (similar to 70-80 degrees C). The thermolysis of complexes 3 or 4 with excess biphenylene and excess alkyne leads to the alkyne cyclotrimerization product as the major organic species formed in the reaction. Fluorenone was catalytically produced by heating (dippe)Ni(CO)(2), biphenylene, and CO. Catalytic insertion of 2,6-xylylisocyanide into the strained C-C bond of biphenylene was also achieved by heating (dippe)Ni(2,6-xylylisocyanide)(2), excess biphenylene, and 2,6-xylylisocyanide. Mechanistic schemes are proposed for these reactions.