Molybdenum complexes coordination numbers

Much of what has been said so far in this chapter applies equally well to complexes of second- and third-row transition metals. However, there are some general differences that result from the fact that atoms and ions of the second- and third-row metals are larger in size than those of first-row metals. For example, because of their larger size (when in the same oxidation state as a first-row ion), ions of metals in the second and third rows form many more complexes in which they have a coordination number greater than 6. Whereas chromium usually has a coordination number of 6, molybdenum forms [Mo(CN)8]4 and other complexes in which the coordination number is 8. Other complexes of second- and third-row metals exhibit coordination numbers of 7 and 9. 

Molybdenum is a metal of the second transition series, one of the few heavy elements known to be essential to life. Its most stable oxidation state, Mo(VI), has 4d orbitals available for coordination with anionic ligands. Coordination numbers of 4 and 6 are preferred, but molybdenum can accommodate up to eight ligands. Most of the complexes are formed from the oxycation Mo(VI)022+. If two molecules of water are coordinated with this ion, the protons are so acidic that they dissociate completely to give Mo(VI)042, the molybdate ion. Other oxidation states vary from Mo(III) to Mo(V). 

Among the metals which have achieved prominence only recently, molybdenum must certainly occupy first place. It has attracted interest chiefly because of its role in biological processes and also because it shows a great variety of oxidation states and coordination numbers. Steifel s extensive review of molybdenum complexes covers their chemistry up to 1977.3 Because of their use in nuclear medicine, the complexes of technetium have received recent interest.4... 

The lanthanide metals, with their larger coordination numbers, invariably have the ligand coordinated in either a trismonodentate or a tetrakismonodentate fashion (42, 55, 57) (see Figs. 10 and 11). Thus, the ligand apparently tends toward the maximization of its coordinating capacity where circumstances allow, giving rise in many cases to the formation of sheet or cage structures. Limited chain formation was observed in the platinum, palladium, and rhodium complexes described, while the molybdenum complexes described by Hilbers et al. consist of dinuclear and tetranuclear units. 

Among the members of the second transition series, molybdenum is the only element definitely known to have specific biological functions. With its ability to exist in oxidation states from 2-to 6+ and coordination numbers ranging from 4 to 8, the metal has an extraordinarily complex chemistry [1]. 

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