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化学学报
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化学学报 ›› 1987, Vol. 45 ›› Issue (7): 636-644. 上一篇    下一篇

研究论文

含烯烃配体的过渡金属卡宾配合物的研究II.异戊二烯二羰基[乙氧基(苯基)卡宾]铁配合物的异构化产物的合成,波谱和结构研究及四羰基[乙氧基(五氯苯基)卡宾]铁的晶体结构

王天兰;陈家碧;徐维铧;章士伟;潘佐华;唐有祺   

  1. 中国科学院上海有机化学研究所;北京大学物理化学研究所
  • 发布日期:1987-07-15

Studies on olefin-coordinating transition metal carbene complexes II. Synthesis, spectral and structural studies of isomerized products of isoprene (dicarbonyl) (ethoxyarylcarbene)iron complexes and crystal structure of tetracarbonyl [ethoxy(pentachloroph

WANG TIANLAN;CHEN JIABI;XU WEIHUA;ZHANG SHIWEI;PAN ZUOHUA;TANG YOUQI   

  • Published:1987-07-15

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异戊二烯三羰基铁(1)与芳基锂ArLi(Ar=C6H5,ρ-CH3C6H4,ρ-CH3OC6H4,ρ-CF3C6H4)在低温下反应,再用Et3OBF4烷基化,可获得组成为C5H8(CO)2FeC(OC2H5)Ar的标题化合物的异构化产物(2一5)。当用LiC6Cl5作亲核试剂,在相同条件下与1反应时,只生成已知的配合物(CO4)FeC(OC2H5)C6Cl5(6)。由单晶X射线衍射数据推断出, 2和6的分子结构都属于单斜晶系,Z=4. 2的空间群为C2h[5]-P21/n,a=8.544(2), b=14.494(5), c=12.309(4)`A,β=96.16(2)`;6的空间群为C2h[5]-P21/c, a=14.126(3), b=6.805(1), c=19.182(5)A,β=103.58(2)`. 2和6的结构用SHELXTL直接法程序解出并经块矩阵最小二乘法修正,R分别为0.066和0.043。

关键词: 晶体结构测定, 红外分光光度法, Ｘ射线衍射分析, 铁络合物, 羰基络合物, 碳烯, 质子磁共振谱法, 锂化合物, 单晶, 过渡金属络合物

Isoprenetricarbonyliron reacts with aryllithium, RLi (R = C6H5, p-CH3C6H4, p-CH3OC6H4, p-CF3C6H4), in ether at low temperature to yield acylmetallate complexes, from which, by subsequent alkylation with Et3OBF4 in aqueous solution at O? the orange-red crystalline complexes with the composition C5H8(CO)2FeC(OC2H5)R (I) formulated as isomerized products of isoprene(dicarbonyl)(ethoxyarylcarbene)iron complexes were obtained. When LiC6Cl5 was used as a nucleophile, the alkylation of acylmetallate intermediate formed under the same conditions gave known complex (CO)4FeC(OC2H5)C6Cl5 (II). The mol. structures of I (R = Ph) and II have been deduced from their single crystal x-ray diffraction data.

Key words: CRYSTAL STRUCTURE DETERMINATION, INFRARED SPECTROPHOTOMETRY, X-RAY DIFFRACTION ANALYSIS, IRON COMPLEX, CARBONYL COMPLEX, CARBENE, PROTON MAGNETIC RESONANCE SPECTROMETRY, LITHIUM COMPOUNDS, SINGLE CRYSTALS, TRANSITION METAL COMPLEX

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