Hyperfine Interactions and Metal Atom Dynamics in a Number of Stannyl Phosphide Compounds and the Detailed Crystal Structure of Triphenyltin Chloride Revisited

Abstract

Temperature-dependent 119 Sn Mössbauer effect (ME) spectroscopy has been used to elucidate the hyperfine parameters (isomer shift and quadrupole splitting) as well as the dynamics of the motion of tin in three triphenyltin phosphide complexes, namely P(SnPh 3 ) 3 (C 54 H 45 PSn 3 , 1), P 7 (SnPh 3 ) 3 (C 54 H 45 P 7 Sn 3 , 2), and [Na(benzo-15-crown-5)][P(SnPh 3 ) 2 ] (C 50 H 50 NaO 5 PSn 2 , 3), as well as in triphenyltin chloride (4). Although the isomer shifts are very similar for all four compounds, the quadrupole splitting is dependent upon their detailed structures. The metal atom vibrations are essentially isotropic with respect to the principal symmetry axis passing through [a]

Spectroscopic and Computational Studies of Spin States of Iron(IV) Nitrido and Imido Complexes

“…The experimental samples were shipped in sealed ampules and transferred in an inert atmosphere glovebox to O-ring sealed Perspex sample holders, which were immediately cooled to liquid-nitrogen temperature and mounted cold in the cryostat. The temperature dependence of the Mössbauer spectra for several of these complexes was also analyzed to provide information on atomic vibrations − as described in Supporting Information. Mössbauer spectra of 3 were recorded at IU-B on a SEE Co. spectrometer.…”

1,16‐Di‐tert‐butyl‐1,16‐diphospha[5.5]ferrocenophane: Synthesis, Reactions and Mössbauer Spectroscopy

“…Dynamics of the iron atom in the diamagnetic compounds: As has been noted previously [35,36] and discussed above, the vibrational amplitudes of the metal atoms in these complexes can be derived from the temperature dependence of the ln A data by making the assumption that in the zero temperature limit the recoil-free fraction reaches unity and that the contribution of the zero point motion in the temperature regime of the ME measurements can be neglected. Validation of these two assumptions has been provided [37] by the detailed comparison of the k 2 < x 2 > parameters over a range of temperatures to the values calculated from the U i,j values extracted from single crystal X-ray measurements over the same temperature range. [37] In the present study, the k 2 < x 2 > values derived from the temperature dependent ME data for 13 have been determined over the available temperature ranges and these data are summarized graphically in Figure 8.…”

“…Validation of these two assumptions has been provided [37] by the detailed comparison of the k 2 < x 2 > parameters over a range of temperatures to the values calculated from the U i,j values extracted from single crystal X-ray measurements over the same temperature range. [37] In the present study, the k 2 < x 2 > values derived from the temperature dependent ME data for 13 have been determined over the available temperature ranges and these data are summarized graphically in Figure 8. It is to be noted that d k 2 < x 2 > /d T is not a linear function over the entire temperature range, implying that at the higher temperatures there is a nonnegligible contribution to this parameter due to low-frequency vibrational or torsional motions of the molecule as a whole.…”