Chapter 19
Diversity of the Nature
of the Nitrogen-Oxygen Bond in Inorganic
and Organic Nitrites in the Light
of Topological Analysis of Electron
Localisation Function (ELF)
Slawomir Berski and Agnieszka J. Gordon
Abstract The electronic structure of nitrite group (–ONO) has been studied for 21
inorganic and organic nitrites using topological analysis of Electron Localisation
Function (ELF) for the DFT(B2PLYP)/aug-cc-pVTZ and DFT(B3LYP)/
aug-cc-pVTZ optimised geometrical structures. The N–O bonds exhibit populations
smaller than 2e, thus including the N
+ O
− , N
− O
+ Lewis-type structures in the
description of electron density delocalisation is of great importance. The main focus
of the ELF analysis was formally single N–O bond in the nitrite group (–O–NO).
The results have yielded four different types of local topology: (a) single local
maximum V(N,O) with the disynaptic bonding basin, (b) two local maxima V(N),
V(O) with monosynaptic non-bonding basins, (c) single local maximum V(N) with
monosynaptic non-bonding basin, (d) absence of the local maxima in the N–O
bond. Analysis of relationships between basin population values, calculated for the
V(N,O), V(N) and V(O) basins, and the N–O bond length, has shown overall trends
that can be qualitatively described by the catastrophe theory.
19.1 Introduction
Electronic structure of compounds, containing the nitrite group (–ONO), namely
inorganic (M–ONO, X–ONO) and organic nitrites (R–ONO) is interesting as they
can serve as NO donors in various chemical and biological systems [1]. Many
organic nitrites act as nitrovasolidators [2, 3] and have been used both clinically [4]
and recreationally [5]. Inorganic nitrites i.e. alkaline nitrites have been studied in the
context of inhibition of steel corrosion process in cement environments [6] or in
S. Berski (&) Á A.J. Gordon
Faculty of Chemistry, University of Wroclaw, F. Joliot-Curie 14,
50-383 Wroclaw, Poland
e-mail: slawomir.berski@chem.uni.wroc.pl
© Springer International Publishing Switzerland 2016
R. Chauvin et al. (eds.), Applications of Topological Methods
in Molecular Chemistry, Challenges and Advances in Computational
Chemistry and Physics 22, DOI 10.1007/978-3-319-29022-5_19
529
Diversity of the Nature
of the Nitrogen-Oxygen Bond in Inorganic
and Organic Nitrites in the Light
of Topological Analysis of Electron
Localisation Function (ELF)
Slawomir Berski and Agnieszka J. Gordon
Abstract The electronic structure of nitrite group (–ONO) has been studied for 21
inorganic and organic nitrites using topological analysis of Electron Localisation
Function (ELF) for the DFT(B2PLYP)/aug-cc-pVTZ and DFT(B3LYP)/
aug-cc-pVTZ optimised geometrical structures. The N–O bonds exhibit populations
smaller than 2e, thus including the N
+ O
− , N
− O
+ Lewis-type structures in the
description of electron density delocalisation is of great importance. The main focus
of the ELF analysis was formally single N–O bond in the nitrite group (–O–NO).
The results have yielded four different types of local topology: (a) single local
maximum V(N,O) with the disynaptic bonding basin, (b) two local maxima V(N),
V(O) with monosynaptic non-bonding basins, (c) single local maximum V(N) with
monosynaptic non-bonding basin, (d) absence of the local maxima in the N–O
bond. Analysis of relationships between basin population values, calculated for the
V(N,O), V(N) and V(O) basins, and the N–O bond length, has shown overall trends
that can be qualitatively described by the catastrophe theory.
19.1 Introduction
Electronic structure of compounds, containing the nitrite group (–ONO), namely
inorganic (M–ONO, X–ONO) and organic nitrites (R–ONO) is interesting as they
can serve as NO donors in various chemical and biological systems [1]. Many
organic nitrites act as nitrovasolidators [2, 3] and have been used both clinically [4]
and recreationally [5]. Inorganic nitrites i.e. alkaline nitrites have been studied in the
context of inhibition of steel corrosion process in cement environments [6] or in
S. Berski (&) Á A.J. Gordon
Faculty of Chemistry, University of Wroclaw, F. Joliot-Curie 14,
50-383 Wroclaw, Poland
e-mail: slawomir.berski@chem.uni.wroc.pl
© Springer International Publishing Switzerland 2016
R. Chauvin et al. (eds.), Applications of Topological Methods
in Molecular Chemistry, Challenges and Advances in Computational
Chemistry and Physics 22, DOI 10.1007/978-3-319-29022-5_19
529