摘要
题示化合物[η~5-{(Me_3Si)_2C_5H_3}Fe(CO)_2]_2(μ-CO)_2分子中的铁铁键被钠汞齐还原断裂,生成相应的单核铁负离子,后者分别与PhCOCl,PhCH_2Cl,ClCH_2COOC_2H_5,Ph_3SnCl及Ph_2SnCl_2进行亲核取代反应,生成在铁原子上引入相应取代基的产物[η~5-{(Me_3Si)_2C_5H_3}Fe(CO)_2R](R:RhCH_2 1,PhCO 2,CH_2COOC_2H_5 3,Ph_3Sn 4和[η~5-{(Me_3Si)_2C_5H_3}Fe(CO)_2]_2SnPh_2 5)。题示化合物分别与卤素和二氯化汞反应,生成铁铁键断裂的铁卤化物和铁氯汞化物[η~5-{(Me_3Si)_2C_5H_3}Fe(CO)_2X](X:Cl 9,Br 6,I 7,HgCl 8)。化合物4的晶体和分子结构经X-射线测定,晶体属单斜晶系,空间群为P2_1/n,晶体学数据:α=1.1261(2),b=1.3077(6),c=2.1017(4)nm;β=101.8(2)°,V=3.2148nm^3,z=4,最终偏差因子R=0.044。
The Fe-Fe bond of the molecule of the title compound {η5-[1,3-(Me3Si)2C5H3] Fe(CO)}2 (μ-CO)2, (A) was cleaved by sodium amalgam and gave the corresponding mononuclear iron anion. The nucleophilic reactions of the anion with variant halides produced respectively the alkylation products on iron atom η-[ 1,3-(Me3Si)2C5H3] Fe(CO)2R(R:PhCH2 1, PhCO 2, CH2COOC2H5 3, Ph3Sn 4, {η-[1,3-(Me3Si)2C5H3] Fe(CO)2}2SnPh2 5). The Fe-Fe bond of A was also cleaved by halogen and HgCl2 and resulted to form derivatives of iron halides and iron chloromecurate η-[ 1,3-(Me3Si)2C5H3]Fe(CO)2X(X: Br 6, I 7, HgCl 8, Cl 9). The crystal stnicture of 4 was determined by X-ray diffraction. The crystal is monoclinic, space group P21 / n with a =1.126(2), b=1.3077(6), c = 2.1017(4)nm; β= 101.8(2)°, V=3.215nm3, z = 4. The final deviation factor R = 0.044.
出处
《有机化学》
SCIE
CAS
CSCD
北大核心
1994年第4期370-375,共6页
Chinese Journal of Organic Chemistry
基金
国家自然科学基金资助的课题
关键词
环戊二烯基
四羧基二铁
Bis(trimethylsilyl)cyclopentadiene, cleavage of Fe-Fe bond, crystal structure
