An elusive goal—that of enforcing the interaction of an electron donor at a polyoxometalate acceptor in solution—has been realized. Covalent tethering of a ferrocenyl group to the hexamolybdate cluster was achieved by the introduction of a ferrocenylimido (FcN) ligand, yielding the anion [(FcN)Mo6O18]2− 1 (shown schematically on the right). The simple synthesis of 1 should also be applicable to other systems and thus may provide new opportunities in the field of charge transfer salts with polyoxometalate anions.

Covalently linked polyoxometalate clusters are produced in the reaction of organic diisocyanates withsuggesting the development of extended interconnected networks incorporating polyoxometalate ions.

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Tetrakis(diphenylmethylphosphine)palladium reacts with diphenylantimony chloride or diphenylbismuth bromide to give [E4(PdL2)4][Ph2EX2]2 (L = PPh2Me, 1:  E = Sb, X = Cl; 2:  E = Bi, X = Br) which have been characterized spectroscopically and by single-crystal X-ray diffraction for [Sb4(PdL2)4][Ph2SbCl2]2·0.5THF and [Bi4(PdL2)4][Ph2BiBr2]2. These compounds are electron-rich based on electron counting formalisms. The additional cluster electrons can be rationalized by the ability of group 15 elements to show hypervalency, particularly those elements such as Sb and Bi which show more metal character. The electronic structure of the compounds and of related species has been examined by EHT and DFT calculations. Relationships to other cubane-derived structures are derived, and the stability of structurally related M4E4 hypothetical clusters is discussed. Compounds 1 and 2 decompose thermally to give Bi2Pd and SbPd.