Oxidative atom-transfer to a trimanganese complex to form Mn 66-E) (E = O, N) clusters featuring interstitial oxide and nitride functionalities

Alison R. Fout, Qinliang Zhao, Dianne J. Xiao, Theodore A. Betley

Research output: Contribution to journalArticlepeer-review

Abstract

Utilizing a hexadentate ligand platform, a trinuclear manganese complex of the type ( HL)Mn 3(thf) 3 was synthesized and characterized ([ HL] 6- = [MeC(CH 2N(C 6H 4-o-NH)) 3] 6-). The pale-orange, formally divalent trimanganese complex rapidly reacts with O-atom transfer reagents to afford the μ 6-oxo complex ( HL) 2Mn 66-O)(NCMe) 4, where two trinuclear subunits bind the central O-atom and the ( HL) ligands cooperatively bind both trinuclear subunits. The trimanganese complex ( HL)Mn 3(thf) 3 rapidly consumes inorganic azide ([N 3]NBu 4) to afford a dianionic hexanuclear nitride complex [( HL) 2Mn 66-N)](NBu 4) 2, which subsequently can be oxidized with elemental iodine to ( HL) 2Mn 66-N)(NCMe) 4. EPR and alkylation of the interstitial light atom substituent were used to distinguish the nitride from the oxo complex. The oxo and oxidized nitride complexes give rise to well-defined Mn(II) and Mn(III) sites, determined by bond valence summation, while the dianionic nitride shows a more symmetric complex, giving rise to indistinguishable ion oxidation states based on crystal structure bond metrics.

Original languageEnglish (US)
Pages (from-to)16750-16753
Number of pages4
JournalJournal of the American Chemical Society
Volume133
Issue number42
DOIs
StatePublished - Oct 26 2011
Externally publishedYes

ASJC Scopus subject areas

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

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