Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Mössbauer Spectroscopic Studies of Trialkyl- and Triaryltin Complexes of Transition Metal Cyanides
Motomi KatadaYoshio UchidaKumiko IwaiHirotoshi SanoHiroshi SakaiYutaka Maeda
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1987 Volume 60 Issue 3 Pages 911-917

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Abstract

The structural diagnosis and lattice dynamics of three complexes, {[R3Sn](μ-NC)[Au(μ-CN)]}x (R=Me, Bu(n-Bu), or Ph), {[R3Sn]2[(μ-NC)4Pt]}x (R=Me, Bu, or Ph), and {[R3Sn]3[(μ-NC)6Fe]}x (R=Bu or Ph) have been undertaken by means of 57Fe-, 119Sn-, and 197Au-Mössbauer spectroscopic techniques. The Mössbauer parameters for the complexes indicate that all the tin atoms are coordinated with three alkyl or aryl groups and two cyano groups having a trigonal–bipyramidal structure. The asymmetry of the quadrupole split-peak intensity observed in the 119Sn-Mössbauer spectra for the complexes was attributed to the anisotropic mean square vibrational amplitude with respect to a molecular symmetry axis. The temperature dependence of the recoil-free fraction of the 119Sn-Mössbauer atom shows that the mean-square vibrational amplitude of tin atoms in the complexes falls in the range of values found for a number of one-dimensional organotin polymers. In 57Fe-Mössbauer spectroscopy, the quadrupole splitting for {[Bu3Sn]3[(μ-NC)6Fe]}x rapidly decreases with an increase in the temperature, reflecting small separations among the three dε levels in energy. The very large 197Au-quadrupole splitting for {[R3Sn](μ-NC)[Au(μ-CN)]}x was explained by assuming strong σ-donating and π-accepting properties of the CN ligand.

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