1H and 31P nuclear spin-lattice relaxation in C-phosphorylated oximes

The 1H spin-lattice relaxation times of the proton-bearing groups and the 31P spin-lattice relaxation times in C-phosphorylated oximes R1C(=NOH)P(=O)R2R3 (R1 = Ph, R2 = R3 = OMe; R1 = Ph, R2 = OMe, R3 = OCH2CH2Br; R1 = PhCH2, R2 = R3 = OCHMe2) and dioxime R2P(=O)C(=NOH)(CH2)4C(=NOH)P(=O)R2 (R = OMe) in DMSO-d6 were measured. The characteristic reorientation times of the whole molecules were estimated using the measured values of the 1H relaxation times and the results of semiempirical PM3 quantum chemical calculations of the molecular geometries. The reorientation times were used to identify the contributions of different relaxation mechanisms to the rate of 31P spin-lattice relaxation. The anisotropy of the chemical shielding of 31P nuclei was evaluated from the difference between the 31P relaxation rates measured at 101.27 and 161.92 MHz.