Oxidative group transfer to a triiron complex to form a nucleophilic μ3-nitride, [Fe33-N)]-

Tamara M. Powers, Alison R. Fout, Shao Liang Zheng, Theodore A. Betley

Research output: Contribution to journalArticlepeer-review

Abstract

Utilizing a hexadentate ligand platform, a high-spin trinuclear iron complex of the type (tbsL)Fe3(thf) was synthesized and characterized ([tbsL]6- = [1,3,5-C6H 9(NPh-o-NSitBuMe2)3]6-). The silyl-amide groups only permit ligation of one solvent molecule to the tri-iron core, resulting in an asymmetric core wherein each iron ion exhibits a distinct local coordination environment. The triiron complex ( tbsL)Fe3(thf) rapidly consumes inorganic azide ([N 3]NBu4) to afford an anionic, trinuclear nitride complex [(tbsL)Fe33-N)]NBu4. The nearly C3-symmetric complex exhibits a highly pyramidalized nitride ligand that resides 1.205(3) Å above the mean triiron plane with short Fe-N (1.871(3) Å) distances and Fe-Fe separation (2.480(1) Å). The nucleophilic nitride can be readily alkylated via reaction with methyl iodide to afford the neutral, trinuclear methylimide complex (tbsL)Fe 33-NCH3). Alkylation of the nitride maintains the approximate C3-symmetry in the imide complex, where the imide ligand resides 1.265(9) Å above the mean triiron plane featuring lengthened Fe-Nimide bond distances (1.892(3) Å) with nearly equal Fe-Fe separation (2.483(1) Å).

Original languageEnglish (US)
Pages (from-to)3336-3338
Number of pages3
JournalJournal of the American Chemical Society
Volume133
Issue number10
DOIs
StatePublished - Mar 16 2011
Externally publishedYes

ASJC Scopus subject areas

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

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