Cluster complexes silyl derivatives

The potential of the synthetic principle described in this article is further illustrated by the observation that other silylated derivatives, such as P(SiMe3)3, can be employed to obtain new clusters. Most recent results show that P(SiMe3)3 will react with CuQ and PEt3, and with [(C4H7)Pd(CO)Br] and PPh3 to form the unusual multinuclear complexes outlined in Scheme 3-30. 

Kai Pii is formed quantitatively from Na3p7 and Pi (in en) in a well defined reaction. The colourless solvate Uai Pii 6en can be obtained from en in crystalline form by counter-current diffusion of THF (Figure 5)- Again we find a solvated molecule or ion-complex Nai Pii in the crystal. The polyanion Pi ", whose trimethyl-silyl substituted derivatives have already been observed in small quantities in mass-spectra ( ), constitutes the first methodically executed step to an oligomerization and finally to a complete polymerization of Pv clusters (I6). 

The most frequently used metallic catalysts for acyldiazo- and (alkoxycarbonyl)dia-zomethanes are complexes or salts of rhodium, palladium and copper. Alkenylboronic esters A-silylated allylamines and acetylenes are successfully cyclopropanat-ed with diazocarbonyl compounds under catalysis of one of those metal derivatives. Newly developed metallic catalysts for diazoacetic esters include polymer-bound, quantitatively recoverable Rh(II) carboxylate salts ", Cu(II) supported on NATION ion exchange poly-mer ruthenacarborane clusters, Rh2(NHCOCH3)4 which produces cyclopropanes with substantially enhanced trans (anti) selectivity as shown below and (rj -CsHs)... 

A variety of sulfide and selenide clusters have been obtained from CpMCE and silylated or Li chalcogenides. The Cp TaS3 unit offers an example of a moiety with three terminal sulfides that might serve as a building block for more complex structures. The presence of the bridging pentasulfide g, ligand, derived from octasulfur, has... 

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