The ground-state rotational spectrum of N,N-diethyl(2H)hydroxylamine (C2H5-NOD-C2H5) was measured by Fourier transform microwave spectroscopy. Six rotational transition lines were assigned to the most stable conformer with the alkyl chain in the trans arrangement and the hydroxyl trans to the bisector of the CNC angle, that is, with the NOD frame in the bc-symmetry plane. Rotational constants are A= 7210.938(2), B= 2018.628(1), and C= 1739.696(1) MHz. These data together with those previously determined for the parent species and 13C and 15N isotopologues, were used to determine a partial r0 structure. The hyperfine structure due to the nuclear quadrupole coupling (NQC) interaction of both 14N and D nuclei was disentangled allowing to obtain the diagonal NQC-constants. On the basis of the determined geometry, the NQC-tensor values in the electric field-gradient principal axis system were determined (χxxN= 0.71, χyyN= 5.90, χzzN= −6.61 MHz; χxxD= −0.11, χyyD= −0.15, χzzD= 0.26 MHz). Comparison with other amines shows that using ammonia as reference, χzzN can be estimated with an additive model: +0.4 and +1.7 MHz from hydrogen to alkyl and hydroxyl substitution, respectively. From the analysis of the available data on the 1:1 water complex of N,N-diethylhydroxylamine, a 8% electric field gradient decrease at the nitrogen nucleus due to the formation of the hydrogen bond involving the nitrogen lone pair was found.

Baroncelli F., Panizzi G., Evangelisti L., Melandri S., Maris A. (2023). Structure and nuclear quadrupole coupling interaction in hydroxylamines: The rotational spectrum of N,N-diethyl(2H)hydroxylamine. JOURNAL OF MOLECULAR SPECTROSCOPY, 392, 1-7 [10.1016/j.jms.2023.111759].

Structure and nuclear quadrupole coupling interaction in hydroxylamines: The rotational spectrum of N,N-diethyl(2H)hydroxylamine

Baroncelli F.;Panizzi G.;Evangelisti L.;Melandri S.;Maris A.
Ultimo
2023

Abstract

The ground-state rotational spectrum of N,N-diethyl(2H)hydroxylamine (C2H5-NOD-C2H5) was measured by Fourier transform microwave spectroscopy. Six rotational transition lines were assigned to the most stable conformer with the alkyl chain in the trans arrangement and the hydroxyl trans to the bisector of the CNC angle, that is, with the NOD frame in the bc-symmetry plane. Rotational constants are A= 7210.938(2), B= 2018.628(1), and C= 1739.696(1) MHz. These data together with those previously determined for the parent species and 13C and 15N isotopologues, were used to determine a partial r0 structure. The hyperfine structure due to the nuclear quadrupole coupling (NQC) interaction of both 14N and D nuclei was disentangled allowing to obtain the diagonal NQC-constants. On the basis of the determined geometry, the NQC-tensor values in the electric field-gradient principal axis system were determined (χxxN= 0.71, χyyN= 5.90, χzzN= −6.61 MHz; χxxD= −0.11, χyyD= −0.15, χzzD= 0.26 MHz). Comparison with other amines shows that using ammonia as reference, χzzN can be estimated with an additive model: +0.4 and +1.7 MHz from hydrogen to alkyl and hydroxyl substitution, respectively. From the analysis of the available data on the 1:1 water complex of N,N-diethylhydroxylamine, a 8% electric field gradient decrease at the nitrogen nucleus due to the formation of the hydrogen bond involving the nitrogen lone pair was found.
2023
Baroncelli F., Panizzi G., Evangelisti L., Melandri S., Maris A. (2023). Structure and nuclear quadrupole coupling interaction in hydroxylamines: The rotational spectrum of N,N-diethyl(2H)hydroxylamine. JOURNAL OF MOLECULAR SPECTROSCOPY, 392, 1-7 [10.1016/j.jms.2023.111759].
Baroncelli F.; Panizzi G.; Evangelisti L.; Melandri S.; Maris A.
File in questo prodotto:
File Dimensione Formato  
jmolspectroscopy.pdf

accesso aperto

Descrizione: Articolo
Tipo: Versione (PDF) editoriale
Licenza: Licenza per Accesso Aperto. Creative Commons Attribuzione (CCBY)
Dimensione 1.03 MB
Formato Adobe PDF
1.03 MB Adobe PDF Visualizza/Apri

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11585/953761
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 2
  • ???jsp.display-item.citation.isi??? 2
social impact