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39252-AC3
Electron Deficient Molecular Clusters of Tetrels and Related Species

Philip P. Power, University of California (Davis)

Work over the past year has been focused on the synthesis of group 14/15 clusters that are stabilized with large groups.  In particular we have concentrated on employing the very bulky primary phosphine ligands of the type H₂PAr' (Ar' = C₆H₃-2,6(C₆H₃-2,6-Prⁱ₂)₂) or H₂PAr* (Ar* = C₆H₃-2,6(C₆H₂-2,4,6-Prⁱ₃)₂) in reactions with various metal amides to yield metal phosphosphinidine clusters.  These reactions are exemplified by the equation

The syntheses were carried out in the absence of a solvent and the products were obtained in almost quantitative yield as dark red, crystalline solids.  They were characterized by ¹H, ¹³C and heteronuclear NMR (³¹P, ¹¹⁹Sn, and ²⁰⁹Pb) NMR spectroscopy.  X-ray crystallography revealed that they possessed dimeric structures with a four-membered M₂P₂ ring core structure.  The rings display folding along the M-----M axis and feature the aryl substituents in a cis-orientation with respect to each other.  These results will be submitted for publication in the near future.  Current work involves the exploration of reactions related to that in eq. (1) using amide derivatives of the transition metals. 

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