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Reactivity of Fe3(CO)(12) with Alkynes R-C≡C-R': Syntheses and Crystal Structures of Substituted Cyclic Ketones and Carbonyl Iron Complexes

Reactivity of Fe_3(CO)_(12) with Alkynes R-C≡C-R': Syntheses and Crystal Structures of Substituted Cyclic Ketones and Carbonyl Iron Complexes
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摘要 The reactivity of carbonyl iron cluster with alkynes has been studied by the thermal reaction of Fe_3(CO)_(12) with R-C≡C-R'(R = Fc(Ferrocenyl); R′ = Ph(Phenyl), Fc, H). The hexacarbonyldiiron cluster with ferracyclopentadiene ring(μ_2, η~4-C_4Ph_4)Fe_2(CO)_6(1) and one tetraphenyl substituted cyclopentadienone(Ph_4C_4CO)(2) were simultaneously obtained by the reaction of Fe_3(CO)_(12) with alkyne(Ph-C≡C-Ph). Only one ferrole cluster(μ_2, η~4-C_4Fc_2H_2)Fe_2(CO)_6(3) was separated by using Fc-C≡C-H as alkyne. One tri-carbonyl iron complex(η~4-C_4Fc_4CO)Fe(CO)_3(4) and an unexpected new cyclic ketone compound 2,2,4,5-tetraferrocenylcyclopenta-4-en-1,3-di-one [Fc_4C_3(CO)_2](5) were obtained by using Fc-C≡C-Fc as alkyne. A new complex(η4-2,4-diphenyl-3,5-diferrocenylcyclopenta-2,4-dien-1-one)-tricarbonyl iron(η~4-C_4Ph_2Fc_2CO)Fe(CO)_3(6) was synthesized by the reaction of Fe_3(CO)_(12) with Fc-C≡C-Ph. The structures of compounds 1~6 were determined by X-ray single-crystal diffraction and spectroscopic characterization. The crystal structures of two new compounds 5 and 6 were analyzed. Our experimental results reveal the structural models of the reaction products are affected by the kinds of substituents from alkynes R-C≡C-R′. The reactivity of carbonyl iron cluster with alkynes has been studied by the thermal reaction of Fe_3(CO)_(12) with R-C≡C-R'(R = Fc(Ferrocenyl); R′ = Ph(Phenyl), Fc, H). The hexacarbonyldiiron cluster with ferracyclopentadiene ring(μ_2, η~4-C_4Ph_4)Fe_2(CO)_6(1) and one tetraphenyl substituted cyclopentadienone(Ph_4C_4CO)(2) were simultaneously obtained by the reaction of Fe_3(CO)_(12) with alkyne(Ph-C≡C-Ph). Only one ferrole cluster(μ_2, η~4-C_4Fc_2H_2)Fe_2(CO)_6(3) was separated by using Fc-C≡C-H as alkyne. One tri-carbonyl iron complex(η~4-C_4Fc_4CO)Fe(CO)_3(4) and an unexpected new cyclic ketone compound 2,2,4,5-tetraferrocenylcyclopenta-4-en-1,3-di-one [Fc_4C_3(CO)_2](5) were obtained by using Fc-C≡C-Fc as alkyne. A new complex(η4-2,4-diphenyl-3,5-diferrocenylcyclopenta-2,4-dien-1-one)-tricarbonyl iron(η~4-C_4Ph_2Fc_2CO)Fe(CO)_3(6) was synthesized by the reaction of Fe_3(CO)_(12) with Fc-C≡C-Ph. The structures of compounds 1~6 were determined by X-ray single-crystal diffraction and spectroscopic characterization. The crystal structures of two new compounds 5 and 6 were analyzed. Our experimental results reveal the structural models of the reaction products are affected by the kinds of substituents from alkynes R-C≡C-R′.
出处 《Chinese Journal of Structural Chemistry》 SCIE CAS CSCD 2017年第4期696-704,共9页 结构化学(英文)
基金 supported by the National Natural Science Foundation of China(Nos.21266019,21062011 and 21462029) Inner Mongolia Autonomous Region Higher Scientific Research Project(NJZY14060)
关键词 substituted cyclopentadienone carbonyl iron complex reactivity of alkyne ferrole complex molecule and crystal structure substituted cyclopentadienone carbonyl iron complex reactivity of alkyne ferrole complex molecule and crystal structure
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