Syntheses and structures of mixed-ligand tetrairon-sulfur clusters, [Cp′2(Ph2C2S2) 2Fe4S4](PF6) and...

Shinji Inomata, Keiichi Hitomi, Hiromi Tobita, Hiroshi Ogino

Research output: Contribution to journalArticlepeer-review

8 Citations (Scopus)

Abstract

Title full: Syntheses and structures of mixed-ligand tetrairon-sulfur clusters, [Cp′2(Ph2C2S2) 2Fe4S4](PF6) and [Cp′3(Ph2C2S2)Fe4 S5](PF6)n (n=1 and 2) (Cp′η5-C5Me5). Structural change of the clusters accompanying electron transfer reactions. The cyclic voltammogram (CV) of the mixed-ligand cubane-type cluster Cp′2(Ph2C2S2)2 Fe4S4 (4) exhibits four reversible one-electron redox waves, corresponding to +2/+1, +1/0, 0/-1, and -1/-2 charged cluster couples. The CV of the mixed-ligand cubane-like cluster Cp′3(Ph2C2S2)Fe4 S5 (5) exhibits four reversible one-electron redox waves, corresponding to +3/+2, + 2/+ 1, + 1/0, and 0/-1 charged cluster couples. Oxidized clusters, [4](PF6)·CH2Cl2, [5](PF62Me2CO and [5](PF6)2·Me2CO, were synthesized by chemical and/of electrochemical methods. The structures of these three salts were determined by X-ray crystallography and compared with those of the parent clusters 4 and 5. Both clusters 4 and 5 shrink as they are oxidized, indicating that the electrons are removed from antibonding orbitals. The crystallographic data are as follows: [4](PF6)·CH2Cl2: orthorhombic, Pna21 with a = 17.259(3), b = 25.682(4), c = 12.628(2) Å, V= 5597(2) Å3, Z = 4 and R = 0.066; [5](PF6)·2Me2CO: triclinic, P1 with a = 14.112(4), b=17.712(3), c=13.325(4) Å, α= 108.08(2), β= 114.74(3), γ=84.00(1)o, V=2874(1) Å3, Z=2 and R=0.066; [5](PF6)2·Me2CO: triclinic, P1 with a=14.985(1), b=15.540(1), c=12.951(1) Å, α=93.40(2), β=95.04(1), γ=96.76(1)o, V=2976(1) Å3, Z=2 and R=0.056.

Original languageEnglish
Pages (from-to)229-238
Number of pages10
JournalInorganica Chimica Acta
Volume225
Issue number1-2
DOIs
Publication statusPublished - 1994 Oct

Keywords

  • Cluster complexes
  • Crystal structures
  • Cyclopentadienyl complexes Mixed-ligand tetrairon-sulfur cluster
  • Electrochemistry
  • Electron transfer
  • Iron complexes
  • Sulfur complexes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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