Molybdenum cluster compounds synthesis

Nitrogenase is another big target of cluster synthesis. The X-ray elucidation of the active center of the Fe-Mo cofactor and P-cluster (5) has accelerated the efforts to find rational preparative methods of trinuclear or cubane-type clusters containing molybdenum (6-9). The raft cores in these cluster complexes are one of the general structural units also in solid-state compounds, and the mutual relationships are very important. A number of review articles are now available on the syntheses, structures, and other properties of metal chalcogenide cluster compounds (6, 7,10-24). 

The thiomolybdate(VI) anions [MoO S4 ] (n = 0-3) have been prepared by a number of methods and, with the exception of [MoOsS] ", act as versatile ligands to a wide variety of metal ions (see Table 1). In each of the compounds listed in this table, the [MoO S4- p ion acts as a bidentate ligand to the metal and the resultant structural versatility has been clearly demonstrated for copper(I) (Table 2). In addition, thiomolybdate(VI) anions are of interest since they have special relevance to aspects of bioinorganic chemistry. Thus, [MoS4] has been widely used in the synthesis of Fe—Mo—S clusters, examples of which serve as spectroscopic analogues for the iron-molybdenum cofactor of the nitrogenases (see Section 36.6.2), and Cu—Mo—S aggregates, which are relevant to the copper deficiency induced by molybdenum in ruminant animals. 

The molybdenum neopentyUdene complex Mo(CHBu )(NR)(OBu )2 is the active catalyst used in a fascinating development for the synthesis of 11-Vt semiconductor clusters (ZnS, CdS, PbS) and silver and gold nanoclusters of predictable size within microdomains in films of block copolymers prepared by ROMP. Block copolymers of norbomene and a functionalized norbomene that wiU complex with a metal-containing compound were prepared and characterized as monodisperse materials. The functionalized component (amine, alkoxide, or thiolate) then sequestered the metal and the metallated block copolymer was cast into a film which was subsequently treated with H2S to convert the metal into the sulfide. The molybdenum complexes have also featured in the development of the synthesis of side-chain liquid crystal polymers by living ROMP.98 99... 

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