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化学学报
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化学学报 ›› 1992, Vol. 50 ›› Issue (4): 409-416. 上一篇    

研究论文

含烯烃配体的过渡金属卡宾配合物的研究 XVIII: 异构化的螺环[4.4]-1,3-壬二烯(二羰基)[乙氧基(芳基)卡宾]铁配合物和螯合烯丙基铁配合物的合成和结构

陈家碧;殷建国;徐维铧   

  1. 中国科学院上海有机化学研究所
  • 发布日期:1992-04-15

Studies on olefin-coordinating transition metal carbene complexes XVIII: Synthesis and structure of isomerized spiro [4.4] nona-1,3-diene (dicarbonyl)[ethoxy(aryl)carbene]iron complexes and chelated allyliron phosphine complexes

CHEN JIABI;YIN JIANGUO;XU WEIHUA   

  • Published:1992-04-15

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螺环[4.4]-1,3-壬二烯三羰基铁(1)与芳基锂试剂, ArLi(Ar=C~6H~5, o-,p-CH~3C~6H~4, p-CH~3OC~6H~4, p-ClC~6H~4, p-C~6H~5C~6H~4)在乙醚中于低温下反应, 生成的酰羰基金属盐用Et~3OBF~4在水溶液中于0℃烷基化生成不稳定的异构化的螺环[4.4]-1,3-壬二烯(二羰基)[乙氧基(芳基)卡宾]铁配合物(2-7)。这些配合物与膦在石油醚中于低温下加成反应, 转变为稳定的膦加成物(8-12)。12的结构经单晶X射线结构分析进一步证实。

关键词: 晶体结构测定, 反应机理, 分子结构, 铁络合物, 螯合物, 膦, 异构体, 烯丙基, 螺环化合物, 壬烯 P

Reaction of spiro[4.4]nona-1,3-diene(tricarbonyl)iron with ArLi (Ar = Ph, o-, p-CH3C6H4, p-CH3OC6H4, p-ClC6H4, p-C6H5C6H4) in ether at low temperature, followed by the alkylation of the resulting acylmetallates with Et3OBF4 in aqueous solution at 0癈 gave the unstable isomerized spiro[4.4]nona-1,3-diene(dicarbonyl)[ethoxy(aryl)carbene]iron complexes, which were transformed into the stable chelated allyliron phosphine adducts e.g., I by the addition reaction with phosphines in petroleum ether at low temperature Crystal structure of I was reported.

Key words: CRYSTAL STRUCTURE DETERMINATION, REACTION MECHANISM, MOLECULAR STRUCTURE, IRON COMPLEX, CHELATES, PHOSPHINE, ISOMER, ALLYL GROUP, SPIRO COMPOUNDS, NONENE P

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