A homologous family of zirconohydrocarbons bearing the 2,2η-biphenyldiyl ligand (biphe) has been prepared. One of the homologues is a tetraanionic zirconate; two are examples of homoleptic η-bound zirconohydrocarbons; three are anionic η complexes. The Zr fragment, assuming a full positive charge on Li, varies from neutral to a remarkable tetraanion. We have found the aryl-aryl bond forming reactivity of these complexes to be interesting, especially for the dianionic and tetranionic complexes. In our initial studies the complexes have shown the ability to undergo 1,2 dicoupling reactions with 1,2-dihaloarenes to form triphenylenes.