Raman spectra and rotational isomerism of dimethylphosphorochloridate and trimethyl phosphate

Taga, Keijiro; Hirabayashi, Noriaki; Yoshida, Tadayoshi; Okabayashi, Hirofumi

doi:10.1016/0022-2860(89)85076-8

Cited by 17 publications

(11 citation statements)

References 23 publications

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“…Several theoretical and experimental studies were devoted to study the molecular structure and related properties of the TMP molecule, including conformational analysis, dipole moments, vibrational frequencies, and barriers for conformer interconversion [46][47][48][49][50][51][52]. Due to its chemical characteristics, TMP is frequently used as nerve gas simulant in the studies and investigations for the destruction of organophosphorus compounds [53,54].…”

Section: Introductionmentioning

confidence: 99%

Adsorption of dimethyl methylphosphonate and trimethyl phosphate on calcium oxide: an ab initio study

2008

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Ab initio study of the adsorption of dimethyl methylphosphonate (DMMP) and trimethyl phosphate (TMP) on three types of models simulating the calcium oxide surface (non-hydroxylated Ca 4 O 4 , completely hydroxylated Ca 4 O 4 (OH) 2 H 2 , and partially hydroxylated Ca 4 O 4 (OH)H) was performed. The target molecule and the surface hydroxyl groups were optimized while the CaO fragment was kept frozen. The intermolecular interactions were investigated applying Bader's Atoms in Molecules theory. The maps of electrostatic potential of the studied adsorption systems were also produced. The interaction energies of studied adsorption systems corrected by the basis set superposition error were obtained. The most energetically favorable adsorption of DMMP and TMP was found at the configuration where the oxygen atoms of the P=O and methoxy groups point toward the Ca cation of the surface. The P atom points toward the O atom of the surface and forms a P-O chemical bond. This configuration was revealed for the non-hydroxylated and partially hydroxylated CaO-DMMP and CaO-TMP systems. The presence and number of surface hydroxyl groups on the CaO models play a key role in the adsorption of the studied compounds. DMMP and TMP were found to be much less stable on the completely hydroxylated CaO surface where they are adsorbed only via weak electrostatic interactions and H-bonding to the surface oxygen atoms and hydroxyl groups. TMP was found to be slightly more stable on this type of surface than DMMP. The difference in stability is even larger if one compares this TMP system with the complex of tabun adsorbed on completely hydroxylated CaO surface model (Michalkova et al. Chem Phys Lett 438:72, 2007).

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Section: Introductionmentioning

confidence: 99%

Adsorption of dimethyl methylphosphonate and trimethyl phosphate on calcium oxide: an ab initio study

2008

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“…P-O-(C) stretching [10], m a PO 3 [17], m a (P-O) 3 [14], m a (P-O 3 ) [9]. This diversity of descriptions reflects the complicated nature of the vibrations in question.…”

Section: -890 CM à1 Regionmentioning

confidence: 99%

“…However, it should be noted that the assignment of the unique signals due to the C s form in the experimental spectra seems extremely difficult. In the work of Taga et al [17], the presence of the C s form is justified by the observation in the liquid phase spectrum of TMP of one, very weak shoulder-band at 440 cm À1 . All the remaining signals that could result from the C s form, are always accompanied by signals due to other (C 3 and/or C 1 ) conformers [14,17].…”

Section: Introductionmentioning

confidence: 99%

“…Finally, there are also vague indications for the possible existence of a third conformer, C s . In particular, two Raman studies [14,17] refer to the experimental observation of three rotational isomers of TMP (C 3 , C s and C 1 ) in the liquid state. However, it should be noted that the assignment of the unique signals due to the C s form in the experimental spectra seems extremely difficult.…”

Section: Introductionmentioning

confidence: 99%

“…In fact, the problem of conformational isomerism in TMP has been addressed many times during several decades. The molecule has been extensively studied in the past using vibrational spectroscopy in solutions [7][8][9][10][11][12][13][14][15][16][17][18][19], in gaseous [18,20] and solid [17][18][19] phases, and isolated in cryogenic matrices [19][20][21][22][23][24]; NMR spectroscopy [14,15,25]; electron diffraction [26]; dipole moments and Kerr constants methods [7,27]; dielectric loss spectroscopy [28]; and theoretically [14,21,[29][30][31]. And this big list of references is far from being complete.…”

Section: Introductionmentioning

confidence: 99%

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Conformational properties of trimethyl phosphate monomer

Reva

Simão

Fausto

2005

Chemical Physics Letters

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Conformational isomerism of trimethylphosphate (TMP) has been studied de novo. TMP monomers were isolated in low temperature xenon matrices at different substrate temperatures and characterized using FTIR spectroscopy. At the lowest temperature, three different conformers, with overall molecular symmetries C 3 , C 1 and C s , were shown to co-exist in the matrix. Increase of the sample temperature led to conformational cooling, with the two minor conformers being depopulated successively, following an order of increasing stability. Initially, the less stable C s conformer converted to the C 1 form and, at higher temperatures, the C 1 conformer converted to the global energy minimum, C 3 . Interpretation of the experimental data was supported by extensive calculations of the vibrational spectra and barriers to the conformational interconversion.

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ChemInform Abstract: Raman Spectra and Rotational Isomerism of Dimethylphosphorochloridate and Trimethyl Phosphate.

et al. 1990

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Raman spectra and rotational isomerism of dimethylphosphorochloridate and trimethyl phosphate

Cited by 17 publications

References 23 publications

Adsorption of dimethyl methylphosphonate and trimethyl phosphate on calcium oxide: an ab initio study

Adsorption of dimethyl methylphosphonate and trimethyl phosphate on calcium oxide: an ab initio study

Conformational properties of trimethyl phosphate monomer

ChemInform Abstract: Raman Spectra and Rotational Isomerism of Dimethylphosphorochloridate and Trimethyl Phosphate.

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