Mononuclear, Nonheme, High-Spin {FeNO} 7/8 Complexes Supported by a Sterically Encumbered N 4 S-Thioether Ligand
The synthesis of a new nonheme iron NO binding complex, [Fe (CH CN)(N3Py SEtCN)](BF ) ( ), is reported. Complex , which contains two sterically encumbering phenyl substituents, exhibits a high-spin (hs) Fe ( = 2) ground state in contrast to the = 0 ground state for unsubstituted [Fe (CH CN)(N3PySEtC...
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| Published in | Inorganic chemistry Vol. 58; no. 15; pp. 9576 - 9580 |
|---|---|
| Main Authors | , , , , |
| Format | Journal Article |
| Language | English |
| Published |
United States
05.08.2019
|
| Online Access | Get full text |
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| Summary: | The synthesis of a new nonheme iron NO binding complex, [Fe
(CH
CN)(N3Py
SEtCN)](BF
)
(
), is reported. Complex
, which contains two sterically encumbering phenyl substituents, exhibits a high-spin (hs) Fe
(
= 2) ground state in contrast to the
= 0 ground state for unsubstituted [Fe
(CH
CN)(N3PySEtCN)(BF
)
. Reaction of
with NO
in CH
CN yields an {FeNO}
(
=
/
) complex
, which slowly decays at 25 °C with loss of NO
to regenerate
. One-electron reduction of
with Cr(C
H
)
at -40 °C yields the metastable,
= 1 {FeNO}
complex
. The nitrosyl moieties in thioether-ligated
and
are significantly less activated than in thiolate-ligated [Fe(NO)(N3PyS)]
, a structurally analogous pair of hs {FeNO}
complexes. Calculations reveal that reduction of
is iron-centered, which may be a general property of hs {FeNO}
complexes. |
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| ISSN: | 0020-1669 1520-510X |
| DOI: | 10.1021/acs.inorgchem.9b01475 |