Heterodinuclear Transition‐Metal Complexes with Multiple Metal–Metal Bonds

Interactions between a pair of transition‐metals can range from weak antiferromagnetic coupling to bonds of the highest multiplicity known in chemistry, for example, quadruple in isolatable compounds. Tremendous effort has been invested in studying homodinuclear transition‐metal–metal bonds. In contrast, relatively little attention has been devoted to heterodinuclear analogues, as it is substantially more challenging to prepare and handle such entities. Yet, in this largely unexplored area of transition‐metal chemistry, novel chemical interactions with unprecedented reactivities are likely to be found. Heterodinuclear analogues of diatomic transition‐metal dimers being yet inaccessible, dinuclear complexes with Werner‐type ligands provide examples of high‐multiplicity bonds between different d elements in their least‐perturbed form. Such compounds provide an opportunity to probe fundamental issues of chemical bonding between transition‐metals, by revealing how and to what extent such bonds are affected by differences in the two metals. Complexes wherein electronically unsaturated heterodinuclear cores are stabilized by π‐acidic ligands (such as CO) hold the potential of new chemical reactions (including catalytic) that capitalize on the synergetic effect of two transition‐metal centers.