过渡金属卡宾配合物——Ⅶ.四羰基[乙氧基(芳基)卡宾]铁配合物的方便合成法

Transition Metal Carbene Complexes Ⅶ. A Convenient Synthesis of Tetracarbonyl ethoxy (aryl)-carbene iron Complexes

五羰基铁,Fe(CO)_5(1),与芳基锂(ArLi)在乙醚中于低温下反应,所生成的酰羰基锂中间体在水溶液中于0℃用Et_3OBF_4烷基化,制得六个标题配合物(C0)_4FeC(OC_2H_5)Ar(Ar:C_6H_5,2;o-CH_3C_6H_4,3;p-CH_3C_6H_4,4;p-CH_3OC_6H_4,5;C_6Cl_5,6;p-CF_3C_6H_4,7).当用p-CF_3C_6H_4Li作为亲核试剂与1反应时,除生成7外,还获得副产物对三氟甲基苯丙酮,p-CF_3C_6H_4COC_2H_5(8).

The six title complexes, (CO)_4FeC (OC_2H_5) Ar (Ar: C_6H_5, 2; o-CH_3C_6H_4, 3; p- CH_8C_6H_4, 4; p-CH_3OC_6H_4, 5; C_6Cl_5, 6; p-CF_3C_6H_4,7), have been prepared by reaction of Fe(CO)_5 (1) with aryllithium (ArLi) in ether at low temperature followed by alkylation of the acylmetalate intermediates formed with Et_3OBF_4 in aqueous solution at 0℃. In the reaction of p-CF_3C_5H_4Li with 1, as a by-product p-trifluoromethylpropiophenone (8) besides the expected complex 7 was obtained.