Characterization of indirect 31P-31P spin-spin coupling and phosphorus chemical shift tensors in pentaphenylphosphinophosphonium tetrachlorogallate, [Ph3P-PPh2][GaCl4]

Phosphorus chemical shift and 31P,31P spin-spin coupling tensors have been characterized for pentaphenylphosphinophosphonium tetrachlorogallate, [Ph3P-PPh2][GaCl4], using solid-state 31P NMR spectroscopy. Spectra obtained with magic-angle spinning yield the isotropic value of the indirect spin-spin coupling, |1J(31P,31P)iso|, 323 ± 2 Hz, while 2D spin-echo and rotational resonance experiments provide the effective dipolar coupling constant, Reff, 1.70 ± 0.02 kHz, and demonstrate that Jiso is negative. Within experimental error, the effective dipolar coupling constant and Jiso are unchanged at –120°C. The anisotropy in 1J(31P,31P), ΔJ, has been estimated by comparison of Reff and the value of the dipolar coupling constant, RDD, calculated from the P—P bond length as determined by X-ray diffraction. It is concluded that |ΔJ| is small, with an upper limit of 300 Hz. Calculations of 1J(31P,31P) for model systems H3P-PH+2 and (CH3)3P-P(CH3)+2 using density functional theory as well as multiconfigurational self-consistent field theory (H3P-PH+2) support this conclusion. The experimental spin-spin coupling parameters were used to analyze the 31P NMR spectrum of a stationary powder sample and provide information about the phosphorus chemical shift tensors. The principal components of the phosphorus chemical shift tensor for the phosphorus nucleus bonded to three phenyl groups are δ11 = 36 ppm, δ22 = 23 ppm, and δ33 = –14 ppm with an experimental error of ±2 ppm for each component. The components are oriented such that δ33 is approximately perpendicular to the P—P bond while δ11 forms an angle of 31° with the P—P bond. For the phosphorus nucleus bonded to two phenyl groups, the principal components of the phosphorus chemical shift tensor are δ11 = 23 ppm, δ22 = –8 ppm, and δ33 = –68 ppm with experimental errors of ±2 ppm. In this case, δ33 is also approximately perpendicular to the P—P bond; however, δ22 is close to the P—P bond for this phosphorus nucleus, forming an angle of 13°. The dihedral angle between the δ33 components of the two phosphorus chemical shift tensors is 25°. Results from ab initio calculations are in good agreement with experiment and suggest orientations of the phosphorus chemical shift tensors in the molecular frame of reference.Key words: Nuclear magnetic resonance spectroscopy, phosphorus chemical shift tensors, 31P-31P J-coupling tensors, density functional theory, multiconfigurational self-consistent field theory, phosphinophosphonium salts.

Konformationsuntersuchungen durch Elektronenspinresonanz Two-Jump-prozesse in Benzyl-phosphonium Salzen / Conformation Studies by Electron Spin Resonance Two-Jump Process in Benzyl-phosphonium Salts

The ESR spectra of 4-oxyl-benzyl-phosphonium-bromide radicals show a temperature dependence of the methylene protons and the phosphorus nucleus coupling constants which is explained by a hindered rotation of the phenoxyl ring of the radicals. Furthermore compounds with different phosphor substituents exhibit the phenomenon of a two jump process. This effect is described by an isomerisation of two symmetric radical conformations. Activation energies for this process are found to be around 7 kcal/Mol. The conformation of the radicals can be discussed as staggered ethane analogues. A lower limit value for the hyperconjugation Bᴾ -parameter is proposed.

Temperaturabhängigkeit der Phosphor-HFS bei Iminophosphoran- Radikalen / Temperature Dependence of ESR-Phosphorus Coupling Constants of Iminophosphorane Radicals

ESR-spectra of iminophosphorane radicals exhibit a strong temperature dependent coupling constant of the phosphorus nucleus. This splitting is described by a superposition of π-σ- and hyperconjugative interactions with the free electron. Because of hindered internal rotation of the iminophosphorane group the hyperconjugation term becomes temperature dependent. Differences in the phosphorus data of ortho- and para-iminophosphorane radicals respectively may be explained by a change of the potential barriers hindering the internal rotation