Mössbauer Spectroscopy of Organometallics: Lattice Dynamics and Structure of Butyltin Compounds

Abstract

The Mossbauer parameters of a number of butyltin compounds have been determined in order to elucidate the relationship between molecular structure and spectroscopic properties of such species. The temperature dependence of the resonance effect magnitude (Debye-Waller factor) has been determined in the range 85 < ~ T < 160 0 K for (BuaSn) 2S04, BUaSnOAc, BuaSnF, and Bu2SnF2, and the isomer shifts and quadrupole splittings at 85°K for these compounds, as well as for Bu2Sn(OAch, are reported. From these data, as well as from the temperature dependent intensity asymmetry (Gol'danskii-Karyagin effect) which is observed in these compounds, a monomeric, binuclear structure is inferred for (BuaSnhS04, in consonance with infrared, mass spectrometric, molecular weight, and solubility data. The Debye-Waller factor for the 1l9Sn resonance in BuaSnOAc which has been recrystallized from CCl 4 is interpreted in terms of a low molecular weight polymeric form for this compound similar to that which has been reported for the "soluble" form of trimethyltin acetate.

A reinvestigation of the structures of organotin sulphates and chromates, including the crystal and molecular structure of bis(trimethyltin) sulphate dihydrate

“…In this case, the low-field resonance arises from tin with co-ordination number four, while the major resonance, at high field, arises from tin with co-ordination number five. That is, even in the solid state, tin atoms with both co-ordination numbers (4,5) exist. Quantitative estimates of site populations by spectral integration are complicated by the rolling baseline, but the 5 : 1 ratio of high:low co-ordination numbers measured gives a good guide.…”

“…C,H,,O,SSn,, M = 459.7, orthorhombic, space group Pbcn (no. 60), u = 11.245 (4), b = 12.695 (5), c = 10.811(4) A, U = 1 543.3 A3, Z = 4, Mo-K, radiation, h = 0.7107 A, D, = 1.98 g cm-,, p = 31.27 mm-', F(000) = 888.…”