Effects of Main-Group and Transition Elements on Bond Formation and Cleavage in Transition-Metal Chalcogenide Clusters: Reactions of E2Fe3(CO)9 (E = Te, Se) with [Co(CO)4], [Mn(CO)5], and [Fe(CO)4]2‒

Minghuey Shieh, Tse Fang Tang, Shie Ming Peng, Gene Hsiang Lee

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The tetrahedral clusters [EFe2Co(CO)9] (E = Te, I; E = Se, II) were synthesized by reactions of the isostructural complexes E2Fe3(CO)9 with [Co(CO)4], respectively. Reaction of Te2Fe3(CO)9 with [Mn(CO)5] gives a Mn(CO)4 bridging butterfly [Te2Fe2Mn(CO)10] (III), while treatment of Se2Fe3(CO)9 with [Mn(CO)5]- produces a square-pyramidal [Se2Fe2Mn(CO)9] (IV). When Te2Fe3(CO)9 reacts with Collman’s reagent, [Fe(CO)4]2− the previously characterized [Te6Fe8(CO)24]2‒ is formed. The similar reaction of Se2Fe3(CO)9 with [Fe(CO)4]2‒ generates the known complexes [SeFe3(CO)9]2‒ and [HSeFe3(CO)9]. The anionic complexes I-IV are fully characterized by infrared spectroscopy, elemental analysis, negative-ion mass, or/and X-ray diffraction methods. Crystals of [Et4N]-[II] are tetragonal, space group P42/ncm with a = 16.456(3) Å, c = 17.925(6) Å, V = 4854(2) Å3, Z = 8, R = 0.045, and Rw = 0.051 at 25 °C. [Et4N][III] crystallizes in the triclinic space group P1 with a = 9.343(3) Å, b = 12.401(6) Å, c = 13.198(2) Å, a = 77.96(3)°, β = 74.36(2)°, y = 69.72(3)°, V = 1370(1) Å3, Z = 2, R = 0.026, and Rw = 0.028 at 25 °C. Crystals of [Et4N][IV] are monoclinic, space group P21/n with a = 9.236(2) Å,b = 24.665(6) Å, c = 11.870(1) Å, β = 112.62(2)°, V = 2496(1) Å3, Z = 4, R = 0.032, and Rw = 0.039 at 25 °C. This paper describes the similarities and differences among these reactions and discusses the effects of the main-group and transition elements on bond formation and cleavage of transition-metal chalcogenide clusters.

Original languageEnglish
Pages (from-to)2797-2803
Number of pages7
JournalInorganic Chemistry
Issue number11
Publication statusPublished - 1995 May 1


ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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