Multimetallic transition metal complexes

The synthesis of multimetallic transition metal complexes where the metals are held at specific distances from each other is an important objective because of their potential role in multimetal-centered catalysis in both biological and industrial reactions (1). Moreover, such systems, through cooperative electronic and/or steric effects between metal centers, might give rise to distinct reactivity patterns for both their stoichiometric and catalytic reactions, which are not available to their monometallic analogues (2). Of the ligands that are able to maintain the metal centers in close proximity, the pyrazolate ion (pz ) appears to be a particularly suitable candidate. Pyrazoles (Hpz ) are weak bases (3, 4) and behave as 2-monohapto ligands. 

Acyclic Schiff base derivatives represent a resourceful class of compartmental ligands which are prepared by self-condensation of appropriate formyl and amine precursors. The condensation reaction is simple and generally leads to the desired product in high yield. Literature data on Lnm mono- and bimetallic complexes, as well as on 4f-d transition metal bimetallic entities with these derivatives are abundant and have been reviewed recently (Vigato and Tamburini, 2004). Extension to multimetallic systems and to complexes with 5f elements... 

Abstract Ruthenium holds a prominent position among the efficient transition metals involved in catalytic processes. Molecular ruthenium catalysts are able to perform unique transformations based on a variety of reaction mechanisms. They arise from easy to make complexes with versatile catalytic properties, and are ideal precursors for the performance of successive chemical transformations and catalytic reactions. This review provides examples of catalytic cascade reactions and sequential transformations initiated by ruthenium precursors present from the outset of the reaction and involving a common mechanism, such as in alkene metathesis, or in which the compound formed during the first step is used as a substrate for the second ruthenium-catalyzed reaction. Multimetallic sequential catalytic transformations promoted by ruthenium complexes first, and then by another metal precursor will also be illustrated. 

One proven way to create these multimetallic molecules is to start with a transition metal (M=Co, Ni, Cu, Zn) salen complex that contains a pendant hydroxyl group in the ortho phenyl position [110-113]. This complex is then treated with one/two equivalents of [U(acac)4] in the presence of pyridine to form the desired mixed metal complexes of the form [ LM (py)2 U ] (L = the hexadentate compartmental ligand Ar,AT -bis(3-hydroxysalicylidene)-... 

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