Multi-site reactivity: Reduction of six equivalents of nitrite to give an Fe 6(NO) 6 cluster with a dramatically expanded octahedral core

T. David Harris, Theodore A. Betley*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

23 Scopus citations

Abstract

Reaction of NO 2 - with the octahedral cluster ( HL) 2Fe 6 in the presence of a proton source affords the hexanitrosyl cluster ( HL) 2Fe 6(NO) 6. This species forms via a proton-induced reduction of six nitrite molecules per cluster, utilizing each site available on the polynuclear core. Formation of the hexanitrosyl cluster is accompanied by a near 2-fold expansion of the ( HL) 2Fe 6 core volume, where intracore Fe-Fe interactions are overcome by strong π-bonding between Fe centers and NO ligands. A core volume of this magnitude is rare in octahedral metal clusters not supported by interstitial atoms. Moreover, the structural flexibility afforded by the ( HL) 2Fe 6 platform highlights the potential for other reaction chemistry involving species with metal-ligand multiple bonds. Carrying out the reaction of the cluster [( HL) 2Fe 6(NCMe) 6] 4+ with nitrite in the absence of a proton source serves to forestall the nitrite reduction and enables clean isolation of the intermediate hexanitro cluster [( HL) 2Fe 6(NO 2) 6] 2-.

Original languageEnglish (US)
Pages (from-to)13852-13855
Number of pages4
JournalJournal of the American Chemical Society
Volume133
Issue number35
DOIs
StatePublished - Sep 7 2011

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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