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

Arynylmagnesium bromides cleave the S? S bond of μ-S₂Fe₂(CO)₆ to give equilibrium mixtures of “open” intermediates (μ-ArC≡CS) (μ-BrMgS)Fe₂(CO)₆ and “closed” intermediates μ-[S(Ar)C=C(MgBr)S]Fe₂(CO)₆. The mixtures were treated with CpFe(CO)₂I or some of organic halides to yield corresponding “open” Fe-S complexes, whereas with CF₃CO₂H, gaseous HBr or CH₃HgCl to afford the “closed” ones. The “closed” products were also observed with those alkyl halides which eliminate HX easily. So, this kind of alkyl halides possibly functions as substrates through elimination of HX in reaction courses     

Syntheses,structures and conformation of butylene-bridged butterfly-shaped Fe-S cluster complexes

Di-Grignard reagent BrMg(CH₂)₄MgBr can reductively cleave the S? S bond of two molecules of μ-S₂Fe₂(CO)₆ to give a double Fe-S cluster core intermediate A which contains a bridging butylene group. Reactions of A with alkyl halides, chloromethyl methyl ether, chloroketones, chloroesters or acyl chlorides in situ give ten structurally novel butylene-bridged double Fe-S core complexes B. For all the complexes B , the structures were confirmed by IR, ¹H NMR and elemental analysis while the conformers of some complexes B were deduced based on related ¹H NMR data. In addition, for Z = Me the structure and conformation of the complex B have been firmly established by an X-ray diffraction technique.     

铁硫和钴碳混合簇配合物μ-[(CO)_6Co_2PhC_2S](μ-RS)Fe_2(CO)_6的合成及表征

本文表明含炔键的单簇铁硫配合物(μ-PhC≡S)(μ-RS)Fe_2CO)_6 1,在乙醚和室温条件下与Co_2(CO)_8发生络合反应,生成铁硫和钴碳双簇配合物μ-[(OC)_5Co_2PhC_2S](μ-RS)Fe_2(CO)_5 2.本文还表征了双簇配合物2的结构并对R与硫桥原子所连的键型以及影响络合反应的空间位阻因素进行了讨论。