Reactions of iron acyl chalcogenide clusters with electrophiles: Reactivity comparison and theoretical calculations

Minghuey Shieh, Yen Yi Chu, Hsin Hung Chi, Horng Sun Chen, Kai Jieah Hsing, Chung Yi Huang

Research output: Contribution to journalArticle

Abstract

The reactions of two types of EFe3-based acyl clusters [EFe 3(CO)9C(O)C(H)CCH2)]∼ (E = S, 1; Se, 2; Te, 3) with different electrophiles have been systematically studied and compared. When the sulfur-substituted allylcarbonyl Fe3-cluster [Fe3(CO) 9{|μ-η213-C(O) CHC(S)CH2}]- (1) was treated with CH3COCl in CH2Cl2, the Fischer-type acyloxy carbene cluster [Fe 3(CO)9{|μ32: η41-C(OCOCH3)-C(H)C(S)CH2}] (4) was obtained, along with the previously reported SC(O)C(CH3)=CH bridged Fe2-complex [Fe2(CO)6{μ-η23-SC(O)C(CH3)CH}] (5) and [HSFe3(CO)9]-. Similar acetylation of the allylcarbonyl SeFe3-cluster [(μ3-Se)Fe 3(CO)931: η13- C(O)C(H)CCH2)]- (2) produced the Fe2-carbene complex [Fe2(CO)6{μ- η|23-C(OCOCH3)C(H)C(Se)CH2}] (6) and the propyne-bridged SeFe3-complex [(μ3-Se)Fe 3(CO)9{|μ-η12: η1-C(CH3)=C(H)}] (7) as well as [HSeFe 3(CO)9]- and [Se2Fe 3(CO)9]. However, when the analogous TeFe 3-based allylcarbonyl cluster [μ3-Te)Fe3(CO) 9(|μ3-η113-C(O) C(H)CCH2)]- (3) reacted with CH3COCl, only the fragmentation product [Te2Fe3(CO)9] was formed. Further acidification of cluster 1 with HBF4 proceeded to form complex 5 and [HSFe3(CO)9]-. Similar acidification of 2 formed the propyne-capped complex 7, however, the protonation of 3 led to the formation of [Te2Fe3(CO)9]. Contrast to the reported reactions of 1 and 3, the reaction of 2 with [Cu(CH3CN) 4][BF4] formed complex 7 and a new C(O)CH=C(Se)(CH 3) bridged Fe2-complex [Fe2(CO)6{μ- η|23-C(O)CHC(Se)(CH3)}] (8). The nature and formation of new carbene complexes 4 and 6 were further elucidated with the aid of molecular orbital calculations at the B3PW91 level of density functional theory.

Original languageEnglish
Pages (from-to)725-734
Number of pages10
JournalJournal of the Chinese Chemical Society
Volume60
Issue number7
DOIs
Publication statusPublished - 2013 Oct 21

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Keywords

  • Acyl
  • Acyloxy
  • Carbene
  • Carbonyl
  • Chalcogen
  • Cluster
  • Iron

ASJC Scopus subject areas

  • Chemistry(all)

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