Quantum chemical approaches to the explanation of differences in NO-donor activity of iron-sulfur nitrosyl complexes

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	https://doi.org/10.1007/s11172-014-0391-3
Publication status	Published - 2014

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)

Access to Document

10.1007/s11172-014-0391-3

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@article{020d364971cb4715a8f31c42635d71bd,

title = "Quantum chemical approaches to the explanation of differences in NO-donor activity of iron-sulfur nitrosyl complexes",

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.",

keywords = "And B3LYP functionals, BP86, Density functional theory, Iron-sulfur nitrosyl complexes, NBO method, NO-donor activity, OPBE, TPSS, Voronoi scheme, Wiberg index",

author = "Emel'yanova, {N. S.} and Poleshchuk, {O. Kh} and Sanina, {N. A.} and Bozhenko, {K. V.} and Aldoshin, {S. M.}",

year = "2014",

doi = "10.1007/s11172-014-0391-3",

language = "English",

volume = "63",

pages = "37--42",

journal = "Russian Chemical Bulletin",

issn = "1066-5285",

publisher = "Springer New York",

number = "1",

}

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

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DO - 10.1007/s11172-014-0391-3

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