Substituent Effects on 31P NMR Chemical Shifts and 1JP-Se of triarylselenophosphates

• Published in: Phosphorus, sulfur, and silicon and the related elements Vol. 185; no. 4; pp. 772 - 784
• Main Authors: Domínguez, Zaira, Hernández, Javier, Silva-Gutiérrez, Lorena, Salas-Reyes, Magali, Sánchez, Mario, Merino, Gabriel
• Format: Journal Article
• Language: English
• Published: ABINGDON Taylor & Francis Group 01.04.2010; Taylor & Francis; Taylor & Francis Ltd
• Subjects: Chemistry; Chemistry, Inorganic & Nuclear; Chemistry, Organic; DFT calculations; NMR; Nuclear magnetic resonance; P NMR; Physical Sciences; Science & Technology; selenophosphates; solvent effect; Studies; AB-INITIO; solvent effect; DFT calculations; DEPENDENCE; TRIMETHYL PHOSPHATE; C-13; RESONANCE; 31P NMR; PART 1; BOND; SPECTRA; selenophosphates; P-31
• DOI: 10.1080/10426500902953979
• ISSN: 1042-6507

The effect of electron-withdrawing (EW) and electron-releasing (ER) substituents on the 31 P NMR chemical shifts and the structural parameters of a series of tris-(p-X-aryl)selenophosphates is reported in this article. Similarly to O-aryl phosphates and O-aryl thiophosphates, EW groups attached to aromatic rings induce a shielding effect on the 31 P NMR signal. After a detailed experimental and theoretical analysis, we confirmed that the selenium atom is the main part responsible for the charge density transfer toward phosphorus through a back-bonding effect. The obtained 1 J P-Se values for the complete series agree with this observation. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.