Substituent effects on the 31P NMR chemical shifts of arylphosphorothionates

• Published in: Tetrahedron Vol. 62; no. 11; pp. 2520 - 2528
• Main Authors: Hernández, Javier, Goycoolea, Francisco M., Zepeda-Rivera, Denisse, Juárez-Onofre, Josué, Martínez, Karla, Lizardi, Jaime, Salas-Reyes, Magali, Gordillo, Bárbara, Velázquez-Contreras, Carlos, García-Barradas, Oscar, Cruz-Sánchez, Samuel, Domínguez, Zaira
• Format: Journal Article
• Language: English
• Published: Elsevier Ltd 01.03.2006
• Subjects: 31P NMR; Ab initio; Arylphosphorothionates; Back-bonding; Propeller-type conformation; X-ray crystal structures; X-ray crystal structures; Arylphosphorothionates; Ab initio; Propeller-type conformation; Back-bonding; 31P NMR
• ISSN: 0040-4020; 1464-5416
• DOI: 10.1016/j.tet.2005.12.053

Six tris(aryloxy)phosphorothionates substituted in the para position of the aromatic rings were synthesized and studied by 31P NMR, X-ray diffraction techniques and ab initio calculations at a RHF/6-31G** level of theory, in order to find the main structural factors associated with the δ 31P in these compounds. As the electron-withdrawing (EW) ability of the substituents was increased, an ‘abnormal’ shielding effect on δ 31P of the arylphosphorothionates was observed. The analyses of the geometrical properties obtained through both experimental and theoretical methods showed that a propeller-type conformation is preferred for the arylphosphorothionates, except in the case of the tris( O-4-methylphenyl)phosphorothionate, since one of the aromatic rings is not rotated in the same direction as the other two in the solid state. The main features associated with the δ 31P NMR of compounds 1– 6 were a decrease of the averaged O–P–O angle and mainly the shortening of the P S bond length, which is consistent with an increase of the thiophosphoryl bond order as δ 31P values go upfield. On the other hand, comparison of the experimental and calculated bond lengths and bond angles involving α bonded atoms to phosphorus of the six compounds suggested that stereoelectronic interactions of the type n πO-σ* P S , n πO-σ* P-OAr and n πS-σ* P-OAr could be present in the arylphosphorothionates 1– 6 . The substituent effects on the 31P NMR chemical shifts of a series of six arylphosphorothionates [S P(OAr) 3] are analyzed in terms of the changes observed in the geometries of the compounds by experimental and theoretical methods.