A Computational Study of the NMR Chemical Shifts of Polynitropyrazoles

The 1H, 13C, 15N, and 17O chemical shifts of 91 nitro-1H-pyrazoles, as well as 1-amino-1H-pyrazole, were calculated using the Gauge-Invariant Atomic Orbital/Becke Three-parameter Lee-Yang-Parr [GIAO/B3LYP/6-311++G(d,p)] method. The majority of these compounds are polynitropyrazoles, including substi...

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Bibliographic Details
Authors: Alcorta, Arturo, Claramunt, Rosa M, Elguero, José, Alkorta, Ibon
Format: article
Status:Published version
Publication Date:2025
Country:España
Institution:Consejo Superior de Investigaciones Científicas (CSIC)
Repository:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/405336
Online Access:http://hdl.handle.net/10261/405336
https://api.elsevier.com/content/abstract/scopus_id/105019198407
Access Level:Open access
Keyword:17O NMR
GIAO/B3LYP/6–311++G(d,p)
amino‐nitro intramolecular hydrogen bonds
nitro‐1H‐pyrazoles
solid‐state NMR effects
Description
Summary:The 1H, 13C, 15N, and 17O chemical shifts of 91 nitro-1H-pyrazoles, as well as 1-amino-1H-pyrazole, were calculated using the Gauge-Invariant Atomic Orbital/Becke Three-parameter Lee-Yang-Parr [GIAO/B3LYP/6-311++G(d,p)] method. The majority of these compounds are polynitropyrazoles, including substituents such as N-nitro, C-nitro, and N-trinitromethyl groups. The calculated chemical shifts were compared with available experimental data using an empirical equation that relates absolute shieldings to chemical shifts. However, a new equation was required to accurately account for the oxygen atoms in the nitro groups. Additionally, some conformational studies were performed to better understand the chemical shifts, particularly those of the OH and NO2 substituents at position 1. Different statistical methods were used to analyze the calculated 15N chemical shifts.