Abstract
The geometries and electronic structures of ironsulfur nitrosyl complexes with aza heterocyclic thiols with μ-SCN bridging ligands, [Fe 2(SCN4Ph)2(NO)4] (1) and [Fe 2(SCN4Me)2(NO)4] (2), were calculated within the framework of the density functional theory (DFT) with the BP86, TPSS, B3LYP, and OPBE functionals in order to explain differ ences in their NOdonor activities. Chemical bonding in the complexes was analyzed using the NBO approach, according to Mulliken, and using the Voronoi scheme. NBO analysis of com plex 1 revealed a strong interaction between orbitals of the lone electron pairs of the Fe atom and the antibonding orbitals of the Fe-N bond which leads to strengthening of the Fe-NO bond. In complex 2, the Fe-NO bond is more polar than in complex 1.
| Original language | English |
|---|---|
| Pages (from-to) | 37-42 |
| Number of pages | 6 |
| Journal | Russian Chemical Bulletin |
| Volume | 63 |
| Issue number | 1 |
| DOIs | |
| Publication status | Published - 2014 |
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Keywords
- And B3LYP functionals
- BP86
- Density functional theory
- Iron-sulfur nitrosyl complexes
- NBO method
- NO-donor activity
- OPBE
- TPSS
- Voronoi scheme
- Wiberg index
ASJC Scopus subject areas
- Chemistry(all)
Cite this
Quantum chemical approaches to the explanation of differences in NO-donor activity of iron-sulfur nitrosyl complexes. / Emel'yanova, N. S.; Poleshchuk, O. Kh; Sanina, N. A.; Bozhenko, K. V.; Aldoshin, S. M.
In: Russian Chemical Bulletin, Vol. 63, No. 1, 2014, p. 37-42.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Quantum chemical approaches to the explanation of differences in NO-donor activity of iron-sulfur nitrosyl complexes
AU - Emel'yanova, N. S.
AU - Poleshchuk, O. Kh
AU - Sanina, N. A.
AU - Bozhenko, K. V.
AU - Aldoshin, S. M.
PY - 2014
Y1 - 2014
N2 - The geometries and electronic structures of ironsulfur nitrosyl complexes with aza heterocyclic thiols with μ-SCN bridging ligands, [Fe 2(SCN4Ph)2(NO)4] (1) and [Fe 2(SCN4Me)2(NO)4] (2), were calculated within the framework of the density functional theory (DFT) with the BP86, TPSS, B3LYP, and OPBE functionals in order to explain differ ences in their NOdonor activities. Chemical bonding in the complexes was analyzed using the NBO approach, according to Mulliken, and using the Voronoi scheme. NBO analysis of com plex 1 revealed a strong interaction between orbitals of the lone electron pairs of the Fe atom and the antibonding orbitals of the Fe-N bond which leads to strengthening of the Fe-NO bond. In complex 2, the Fe-NO bond is more polar than in complex 1.
AB - The geometries and electronic structures of ironsulfur nitrosyl complexes with aza heterocyclic thiols with μ-SCN bridging ligands, [Fe 2(SCN4Ph)2(NO)4] (1) and [Fe 2(SCN4Me)2(NO)4] (2), were calculated within the framework of the density functional theory (DFT) with the BP86, TPSS, B3LYP, and OPBE functionals in order to explain differ ences in their NOdonor activities. Chemical bonding in the complexes was analyzed using the NBO approach, according to Mulliken, and using the Voronoi scheme. NBO analysis of com plex 1 revealed a strong interaction between orbitals of the lone electron pairs of the Fe atom and the antibonding orbitals of the Fe-N bond which leads to strengthening of the Fe-NO bond. In complex 2, the Fe-NO bond is more polar than in complex 1.
KW - And B3LYP functionals
KW - BP86
KW - Density functional theory
KW - Iron-sulfur nitrosyl complexes
KW - NBO method
KW - NO-donor activity
KW - OPBE
KW - TPSS
KW - Voronoi scheme
KW - Wiberg index
UR - http://www.scopus.com/inward/record.url?scp=84906848382&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84906848382&partnerID=8YFLogxK
U2 - 10.1007/s11172-014-0391-3
DO - 10.1007/s11172-014-0391-3
M3 - Article
VL - 63
SP - 37
EP - 42
JO - Russian Chemical Bulletin
JF - Russian Chemical Bulletin
SN - 1066-5285
IS - 1
ER -