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

doi:10.1021/acs.inorgchem.9b01475

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

Chemical Physiology and Biochemistry

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Abstract

The synthesis of a new nonheme iron NO binding complex, [Fe^II(CH₃CN)(N3Py^2PhSEtCN)](BF₄)₂ (1), is reported. Complex 1, which contains two sterically encumbering phenyl substituents, exhibits a high-spin (hs) Fe^II (S = 2) ground state in contrast to the S = 0 ground state for unsubstituted [Fe^II(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 language	English (US)
Pages (from-to)	9576-9580
Number of pages	5
Journal	Inorganic Chemistry
Volume	58
Issue number	15
DOIs	https://doi.org/10.1021/acs.inorgchem.9b01475
State	Published - Aug 5 2019

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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

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.",

author = "Confer, {Alex M.} and Sinan Sabuncu and Siegler, {Maxime A.} and Pierre Mo{\"e}nne-Loccoz and Goldberg, {David P.}",

note = "Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",

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AU - Confer, Alex M.

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AU - Siegler, Maxime A.

AU - Moënne-Loccoz, Pierre

AU - Goldberg, David P.

PY - 2019/8/5

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N2 - 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.

AB - 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.

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

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