Experimental and theoretical vibrational study of isatin, its 5-(NO2, F, Cl, Br, I, CH3) analogues and the isatinato anion

Pance Naumov, Frosa Anastasova

Research output: Contribution to journalArticle

Abstract

Effects of 5-R substitution (R = NO2, F, Cl, Br, I, CH3) and N-deprotonation on the 4000-400 cm-1 region of the low temperature FT IR spectrum and the molecular structure of solid isatin are investigated. Harmonic IR spectra and molecular geometries of the 5-R isatins (except for Br and I analogues) are calculated at the HF/6-31G(d, p) level and compared with the experimental solid-state data. In general, substitution has small effect on the molecular structure and the IR spectrum of isatin. The ν(CO) triplet in the IR spectra of isatin and its 5-substituted analogues is resulted by vibrational splitting of the out-of-phase CO stretching, νop[(CO)2]. While the frequency of the νop[(CO)2] mode is relatively less affected by 5-substitution and mainly depends on the substituent mass, the frequency of the in-phase stretching, νip[(CO)2], is strongly sensitive to both mass and electronic properties of the substituent. Substitution at C5 has relatively greater influence on the electron density and the force constant of the amide than on the ketone carbonyl group. Strong electron-donors shorten and stabilize the unusually long α-dicarbonyl CC bond, while electron-accepting groups tend to stretch this bond further. N-Deprotonation brings to elongation of the five membered-ring along the N-CCO(ketone) vector and expansion of the bonds within the α-dicarbonyl part. Theoretical ν(CO) frequency of isatin is lowered for about 180 cm-1 upon conversion into isatinato ion. Harmonic vibrational analysis reveals that only the highest-frequency ν(CO) mode of the isolated isatinato anion can be considered good group vibration for empirical assignments in spectra of solid isatinates. Owing to the solid-state influences on the ν[(CO)2] modes, no reliable spectra-structure correlations could be established from the present experimental spectroscopic data.

Original languageEnglish (US)
Pages (from-to)469-481
Number of pages13
JournalSpectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy
Volume57
Issue number3
DOIs
StatePublished - Mar 1 2001

Fingerprint

Isatin
Carbon Monoxide
Anions
Substitution reactions
Negative ions
analogs
anions
Deprotonation
Ketones
substitutes
Molecular structure
Stretching
ketones
Electrons
molecular structure
Amides
Electronic properties
solid state
Carrier concentration
harmonics

ASJC Scopus subject areas

  • Analytical Chemistry
  • Atomic and Molecular Physics, and Optics
  • Instrumentation
  • Spectroscopy

Cite this

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title = "Experimental and theoretical vibrational study of isatin, its 5-(NO2, F, Cl, Br, I, CH3) analogues and the isatinato anion",
abstract = "Effects of 5-R substitution (R = NO2, F, Cl, Br, I, CH3) and N-deprotonation on the 4000-400 cm-1 region of the low temperature FT IR spectrum and the molecular structure of solid isatin are investigated. Harmonic IR spectra and molecular geometries of the 5-R isatins (except for Br and I analogues) are calculated at the HF/6-31G(d, p) level and compared with the experimental solid-state data. In general, substitution has small effect on the molecular structure and the IR spectrum of isatin. The ν(CO) triplet in the IR spectra of isatin and its 5-substituted analogues is resulted by vibrational splitting of the out-of-phase CO stretching, νop[(CO)2]. While the frequency of the νop[(CO)2] mode is relatively less affected by 5-substitution and mainly depends on the substituent mass, the frequency of the in-phase stretching, νip[(CO)2], is strongly sensitive to both mass and electronic properties of the substituent. Substitution at C5 has relatively greater influence on the electron density and the force constant of the amide than on the ketone carbonyl group. Strong electron-donors shorten and stabilize the unusually long α-dicarbonyl CC bond, while electron-accepting groups tend to stretch this bond further. N-Deprotonation brings to elongation of the five membered-ring along the N-CCO(ketone) vector and expansion of the bonds within the α-dicarbonyl part. Theoretical ν(CO) frequency of isatin is lowered for about 180 cm-1 upon conversion into isatinato ion. Harmonic vibrational analysis reveals that only the highest-frequency ν(CO) mode of the isolated isatinato anion can be considered good group vibration for empirical assignments in spectra of solid isatinates. Owing to the solid-state influences on the ν[(CO)2] modes, no reliable spectra-structure correlations could be established from the present experimental spectroscopic data.",
author = "Pance Naumov and Frosa Anastasova",
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TY - JOUR

T1 - Experimental and theoretical vibrational study of isatin, its 5-(NO2, F, Cl, Br, I, CH3) analogues and the isatinato anion

AU - Naumov, Pance

AU - Anastasova, Frosa

PY - 2001/3/1

Y1 - 2001/3/1

N2 - Effects of 5-R substitution (R = NO2, F, Cl, Br, I, CH3) and N-deprotonation on the 4000-400 cm-1 region of the low temperature FT IR spectrum and the molecular structure of solid isatin are investigated. Harmonic IR spectra and molecular geometries of the 5-R isatins (except for Br and I analogues) are calculated at the HF/6-31G(d, p) level and compared with the experimental solid-state data. In general, substitution has small effect on the molecular structure and the IR spectrum of isatin. The ν(CO) triplet in the IR spectra of isatin and its 5-substituted analogues is resulted by vibrational splitting of the out-of-phase CO stretching, νop[(CO)2]. While the frequency of the νop[(CO)2] mode is relatively less affected by 5-substitution and mainly depends on the substituent mass, the frequency of the in-phase stretching, νip[(CO)2], is strongly sensitive to both mass and electronic properties of the substituent. Substitution at C5 has relatively greater influence on the electron density and the force constant of the amide than on the ketone carbonyl group. Strong electron-donors shorten and stabilize the unusually long α-dicarbonyl CC bond, while electron-accepting groups tend to stretch this bond further. N-Deprotonation brings to elongation of the five membered-ring along the N-CCO(ketone) vector and expansion of the bonds within the α-dicarbonyl part. Theoretical ν(CO) frequency of isatin is lowered for about 180 cm-1 upon conversion into isatinato ion. Harmonic vibrational analysis reveals that only the highest-frequency ν(CO) mode of the isolated isatinato anion can be considered good group vibration for empirical assignments in spectra of solid isatinates. Owing to the solid-state influences on the ν[(CO)2] modes, no reliable spectra-structure correlations could be established from the present experimental spectroscopic data.

AB - Effects of 5-R substitution (R = NO2, F, Cl, Br, I, CH3) and N-deprotonation on the 4000-400 cm-1 region of the low temperature FT IR spectrum and the molecular structure of solid isatin are investigated. Harmonic IR spectra and molecular geometries of the 5-R isatins (except for Br and I analogues) are calculated at the HF/6-31G(d, p) level and compared with the experimental solid-state data. In general, substitution has small effect on the molecular structure and the IR spectrum of isatin. The ν(CO) triplet in the IR spectra of isatin and its 5-substituted analogues is resulted by vibrational splitting of the out-of-phase CO stretching, νop[(CO)2]. While the frequency of the νop[(CO)2] mode is relatively less affected by 5-substitution and mainly depends on the substituent mass, the frequency of the in-phase stretching, νip[(CO)2], is strongly sensitive to both mass and electronic properties of the substituent. Substitution at C5 has relatively greater influence on the electron density and the force constant of the amide than on the ketone carbonyl group. Strong electron-donors shorten and stabilize the unusually long α-dicarbonyl CC bond, while electron-accepting groups tend to stretch this bond further. N-Deprotonation brings to elongation of the five membered-ring along the N-CCO(ketone) vector and expansion of the bonds within the α-dicarbonyl part. Theoretical ν(CO) frequency of isatin is lowered for about 180 cm-1 upon conversion into isatinato ion. Harmonic vibrational analysis reveals that only the highest-frequency ν(CO) mode of the isolated isatinato anion can be considered good group vibration for empirical assignments in spectra of solid isatinates. Owing to the solid-state influences on the ν[(CO)2] modes, no reliable spectra-structure correlations could be established from the present experimental spectroscopic data.

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JO - Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy

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