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. 2021 Feb 20;26(4):1144.
doi: 10.3390/molecules26041144.

Complexes of Formaldehyde and α-Dicarbonyls with Hydroxylamine: FTIR Matrix Isolation and Theoretical Study

Barbara Golec  1 , Magdalena Sałdyka  2 , Zofia Mielke  2
Affiliations

Complexes of Formaldehyde and α-Dicarbonyls with Hydroxylamine: FTIR Matrix Isolation and Theoretical Study

Barbara Golec et al. Molecules. .

Abstract

The interactions of formaldehyde (FA), glyoxal (Gly) and methylglyoxal (MGly) with hydroxylamine (HA) isolated in solid argon and nitrogen were studied using FTIR spectroscopy and ab initio methods. The spectra analysis indicates the formation of two types of hydrogen-bonded complexes between carbonyl and hydroxylamine in the studied matrices. The cyclic planar complexes are stabilized by O-H⋯O(C), and C-H⋯N interactions and the nonplanar complexes are stabilized by O-H⋯O(C) bond. Formaldehyde was found to form with hydroxylamine, the cyclic planar complex and methylglyoxal, the nonplanar one in both argon and nitrogen matrices. In turn, glyoxal forms with hydroxylamine the most stable nonplanar complex in solid argon, whereas in solid nitrogen, both types of the complex are formed.

Keywords: carbonyls; computational chemistry; hydrogen bond; hydroxylamine; matrix isolation; vibrational spectroscopy.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
The optimized structures of the HCHO–NH2OH complexes, IFH–VFH. The ∆ECP(ZPE)-binding energies in kJ mol−1 are given in parentheses. The intermolecular distances are given in Å.
Figure 2
Figure 2
The spectra of the HCHO/Ar (a), NH2OH/Ar (b) and HCHO/NH2OH/Ar (c) matrices recorded after matrix deposition at 11 K. The bands of the HCHO–NH2OH complex are marked by the arrows.
Figure 3
Figure 3
The optimized structures of the CHOCHO–NH2OH complexes, IGH–IVGH. The ∆ECP (ZPE)-binding energies in kJ mol−1 are given in parentheses. The intermolecular distances are given in Å.
Figure 4
Figure 4
The spectra of the CHOCHO/Ar (a), NH2OH/Ar (b) and CHOCHO/NH2OH/Ar (c) matrices recorded after matrix deposition at 11 K. The bands of the CHOCHO–NH2OH complex are indicated by the arrows.
Figure 5
Figure 5
The spectra of the CHOCHO/N2 (a), NH2OH/N2 (b) and CHOCHO/NH2OH/N2 (c) matrices recorded after matrix deposition at 11 K. The bands of CHOCHO–NH2OH complexes are indicated by the arrows. Solid and dashed arrows correspond to the IIIGH and IGH structures, respectively.
Figure 6
Figure 6
The optimized structures of the CH3COCHO–NH2OH complexes, IMHk–IVMHk and IMHa–IVMHa. The intermolecular distances are given in Å. The ∆ECP(ZPE)-binding energies in kJ mol−1 are given in parentheses.
Figure 7
Figure 7
The spectra of the CH3COCHO/Ar (a), NH2OH/Ar (b) and CH3COCHO/NH2OH/Ar (c) matrices recorded after matrix deposition at 11 K. The bands of the CH3COCHO–NH2OH complex are indicated by the arrows.
Figure 8
Figure 8
The spectra of the CH3COCHO/N2 (a), NH2OH/N2 (b) and CH3COCHO/NH2OH/N2 (c) matrices recorded after matrix deposition at 11 K. The bands of CH3COCHO–NH2OH complex are indicated by the arrows.
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