Mononuclear, nonheme, high-spin {FeNO}7/8 complexes supported by a sterically encumbered N4S-T.

Alex M. Confer, Sinan Sabuncu, Maxime A. Siegler, Pierre Moënne-Loccoz, David P. Goldberg

Research output: Contribution to journalArticle

1 Scopus citations

Abstract

The synthesis of a new nonheme iron NO binding complex, [FeII(CH3CN)(N3Py2PhSEtCN)](BF4)2 (1), is reported. Complex 1, which contains two sterically encumbering phenyl substituents, exhibits a high-spin (hs) FeII (S = 2) ground state in contrast to the S = 0 ground state for unsubstituted [FeII(CH3CN)(N3PySEtCN)(BF4)2. Reaction of 1 with NO(g) in CH3CN yields an {FeNO}7 (S = 3/2) complex 2, which slowly decays at 25 °C with loss of NO. to regenerate 1. One-electron reduction of 2 with Cr(C6H6)2 at-40 °C yields the metastable, S = 1{FeNO}8 complex 3. The nitrosyl moieties in thioether-ligated 2 and 3 are significantly less activated than in thiolate-ligated [Fe(NO)(N3PyS)]+/0, a structurally analogous pair of hs {FeNO}7/8 complexes. Calculations reveal that reduction of 2 is iron-centered, which may be a general property of hs {FeNO}7/8 complexes.

Original languageEnglish (US)
Pages (from-to)9576-9580
Number of pages5
JournalInorganic Chemistry
Volume58
Issue number15
DOIs
StatePublished - Aug 5 2019

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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