Reductive assembly of cyclobutadienyl and diphosphacyclobutadienyl rings at uranium

Despite the abundance of f-block–cyclopentadienyl, arene, cycloheptatrienyl and cyclo-octatetraenide complexes, cyclobutadienyl derivatives are unknown in spite of their prevalence in the d-block. Here we report that reductive [2+2]-cycloaddition reactions of diphenylacetylene and (2,2-dimethylpropylidyne)phosphine with uranium(V)-inverted sandwich 10π-toluene tetra-anion complexes results in the isolation of inverted sandwich cyclobutadienyl and diphosphacyclobutadienyl dianion uranium(IV) complexes. Computational analysis suggests that the bonding is predominantly electrostatic. Although the ψ4 molecular orbital in the cyclobutadienyl and diphosphacyclobutadienyl ligands exhibits the correct symmetry for δ-bonding to uranium, the dominant covalent contributions arise from π-bonding involving ψ2 and ψ3 orbital combinations. This contrasts with uranium complexes of larger arenes and cyclo-octatetraenide, where δ-bonding dominates. This suggests that the angular requirements for uranium to bond to a small four-membered ring favours π-bonding, utilizing 5f- instead of 6d-orbitals, over δ-bonding that is favoured with larger ligands, where 6d-orbitals can become involved in the bonding.