Photochemical Alkyne Insertions into the Iron–Thiocarbonyl Bond of [Fe2(CS)(CO)3(Cp)2]
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https://figshare.com/articles/dataset/Photochemical_Alkyne_Insertions_into_the_Iron_Thiocarbonyl_Bond_of_Fe_sub_2_sub_CS_CO_sub_3_sub_Cp_sub_2_sub_/3520100
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Internal alkynes (RCCR) react with [Fe2(CS)(CO)3(Cp)2] (1), under UV radiation, to give the complexes [Fe2{μ-η1:η3-C(R)C(R)CS}(μ-CO)(CO)(Cp)2] [R = Et, 2a; R = Ph, 2b; R = CO2Me, 2c], as a result of CO displacement and alkyne insertion into the metal–CS bond of 1. In addition, the reaction of 1 with EtCCEt affords the metallacycle species [Fe2{μ-η2:η2-C(S)C(Et)C(Et)C(O)}(CO)2(Cp)2] (3) as secondary product. The molecular structures of 2a and 3 have been elucidated by X-ray diffraction studies. Compound 1 reacts with HCCCO2Me, affording the complex [Fe2{μ-η1:η3-C(H)C(CO2Me)CS}(μ-CO)(CO)(Cp)2] (2d) in modest yield. Complexes 2a,b undergo selective methylation at the sulfur atom, generating the cationic complexes [Fe2{μ-η1:η3-C(R)C(R)C(SMe)}(CO)(μ-CO)(Cp)2][CF3SO3] [R = Et, 4a; R = Ph, 4b]. The X-ray structure of 4a has also been determined. Finally, 4b undergoes nucleophilic addition of hydride and cyanide (from NaBH4 and NBun4CN, respectively) to form the vinylalkylidene complexes [Fe2{μ-η1:η3-C(Ph)C(Ph)C(X)(SMe)}(CO)(μ-CO)(Cp)2] [X = H, 5; X = CN, 6].
创建时间：
2016-08-16
