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化学学报
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化学学报 ›› 1988, Vol. 46 ›› Issue (12): 1175-1180. 上一篇    下一篇

研究论文

μ-联硫六羰基二铁与芳炔基Grignard试剂加成反应的研究 - “开环”和“闭环”铁硫原子簇配合物的合成、结构及形成机理

宋礼成;王中夏;KATIATA MBIYANGANDU;王积涛   

  1. 南开大学化学系
  • 发布日期:1988-12-15

Studies on addition of arynyl grignard reagents to (m-dithio)bis (tricarbonyliron) - Synthesis, structures and and formation mechanism of “open”and “closed” iron-sulfur cluster complexes

SONG LICHENG;WANG ZHONGXIA;KATIATA MBIYANGANDU;WANG JITAO   

  • Published:1988-12-15

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芳炔基溴化镁断裂μ-S2Fe2(CO)6的S-S键生成“开环”中间物(μ-ArC≡CS)(μ-BrMgS)Fe(CO)6D及“闭环”中间物μ-[S(Ar)C=C(MgBr)S]Fe2(CO)6E的平衡混合物. 该混合物用Cp(CO)2FeI或某些卤代物处理后生成相应的“开环”铁硫配合物;用CF3CO2H, HBr气体及CH3HgCl处理则得相应“闭环”铁硫配合物; 在与易消除卤化氢的卤代烃反应时也生成“闭环”配合物, 这类卤代烃可能是按消除HX过程而起作用; 对可能的机理进行了讨论.

关键词: 反应机理, 铁络合物, 羰基络合物, 簇状化合物, 过渡金属络合物, 加成反应, 硫络合物, 格氏试剂, 开环

Arynylmagnesium bromides cleave the S-S bond of m-S2Fe2(CO)6 to give an equilibrium, mixtures of open intermediates (m-ArCYCS)(m-BrMgS)Fe2CO)6 and closed intermediates m-[S(Ar)C:C(MgBr)S]Fe2(CO)6. The mixtures were treated with CpFe(CO)2I (Cp = cyclopentadienyl) or some organic halides to yield the corresponding open Fe-S complexes, whereas with CF3CO2H, gaseous HBr or CH3HgCl the treated mixtures afford the closed ones. The closed products were also observed with those alkyl halides which eliminate HX easily. This kind of alkyl halides possibly functions as substrates through elimination of HX during the course of reaction.

Key words: REACTION MECHANISM, IRON COMPLEX, CARBONYL COMPLEX, CLUSTER COMPOUND, TRANSITION METAL COMPLEX, ADDITION REACTION, SULFIDE COMPLEX, GRIGNARD REAGENT, OPEN CYCLE

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