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Conversion of (R4N+)4[S4M4(SPh)16]4− Molecular Solids to Bulk Metal Sulfides

Published online by Cambridge University Press:  15 February 2011

W. E. Farneth ,
N. Herron  and
Y. Wang
W. E. Farneth
Affiliation:
Du Pont, Central Research and Development, Experimental Station, P. O. Box 80356, Wilmington, DE 19880-0356
N. Herron
Affiliation:
Du Pont, Central Research and Development, Experimental Station, P. O. Box 80356, Wilmington, DE 19880-0356
Y. Wang
Affiliation:
Du Pont, Central Research and Development, Experimental Station, P. O. Box 80356, Wilmington, DE 19880-0356
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Abstract

In this paper we report on the mechanism of the solid state conversion of a series of IINI precursors of general formula (R4N+)4[S4M4(SPh)16]4− (R=Me, Et; M=Cd, Zn) to the bulk metal sulfide structure. This family of cluster compounds was first reported by Dance et al [1]. On heating these solids in vacuum or inert atmosphere, we find that they convert to the corresponding extended metal sulfide lattice in two discrete reaction steps. The overall reaction appears to be general, but there are interesting differences in the rates and mechanistic details as R and M are varied. The first step, ˜200°C, can be characterized as a nucleophilic substitution or elimination initiated by the attack of a fragment of the anion cluster on the tetra-alkyl ammonium counterion. The intermediate solid produced in this step has been isolated and recrystallized. It consists of charge neutral M10S16Ph12 clusters that retain the cluster size present in the starting material but appear to aggregate to varying degrees in the solid or solution.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 272: Symposium O – Chemical Processes in Inorganic Materials: Metal and Semiconductor Clusters , 1992 , 47
Copyright
Copyright © Materials Research Society 1992

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References

REFERENCES

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