Ternary antimony–chalcogen iron carbonyl complexes and their derivatives: Syntheses, structures, reactivities, and low-energy-gap characteristics

Hsin Hung Yeh, Ming Chi Hsu, Yu Huei Li, Yi No Hsu, Fang Yu Shr, Minghuey Shieh

Research output: Contribution to journalArticlepeer-review

Abstract

A novel series of ternary antimony–chalcogen iron carbonyl clusters, [{SbTeFe3(CO)9}{Te2Fe3(CO)9}] (1), [{SbSeFe3(CO)9}{Se2Fe2(CO)6}] (2), and [{SbSFe3(CO)9}{SFe3(CO)9}] (3), were synthesized in moderate yields from reactions of [EFe3(CO)9]2– (E = Te, Se, S) with SbCl3. X-ray analyses revealed that complexes 1–3 each can be viewed as a square pyramidal geometry [SbEFe3(CO)9] (E = Te, Se, S), where the Sb atom was further coordinated with pendant cluster fragments [Te2Fe3(CO)9], [Se2Fe2(CO)6], and [SFe3(CO)9], respectively. Interestingly, the oxidation state of the Sb atom in complexes 1–3 was 0, which was evidenced by XPS and XANES. Complexes 1–3 showed high electrophilicity toward a series of metal carbonylates, which produced transmetallated products, the “spiked” square pyramidal complexes [{SbEFe3(CO)9}{M(CO)x}] [M(CO)x = Fe(CO)4, E = Te, 1-Fe; Se, 2-Fe; S, 3-Fe; M(CO)x = Cr(CO)5, Se, 2-Cr; S, 3-Cr] and the Mn(CO)4-bridged di-ESbFe3(CO)9-based clusters [{SbEFe3(CO)9}2Mn(CO)4] (E = Se, 2-Mn; S, 3-Mn). Furthermore, the diffuse reflectance spectra showed that these ternary and quaternary antimony-chalcogenide metal carbonyl clusters possessed low energy gaps of 0.84–1.48 eV, suggesting possible electron transports within the frameworks, which was supported by crystal packings and DFT calculations.

Original languageEnglish
Article number121717
JournalJournal of Organometallic Chemistry
Volume937
DOIs
Publication statusPublished - 2021 Apr 1
Externally publishedYes

Keywords

  • Antimony
  • Carbonyl
  • Chalcogen
  • Heterometallic
  • Iron

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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