Supramolecular organometallic chemistry: the platinum(IV) paradigm

Supramolecular chemistry and the chemistry of alkyl derivatives of the transition metals are both topics of considerable current interest, but the combination of the two fields is still underdeveloped. The challenges are, in large part, experimental in nature. For example, the self-assembly of molecules in supramolecular chemistry often relies on intermolecular hydrogen bonding, but most alkyl-transition metal bonds are cleaved by the protic groups used in hydrogen bond formation. Alkyl-platinum(IV) bonds are inert to protonolysis or attack by other electrophiles under mild conditions, and this has allowed an extensive supramolecular chemistry of organoplatinum(IV) complexes to be developed, as outlined in this perspective review. Highlights include a zeolitic structure, a polyrotaxane, a double helix, a nanotube structure and an example of spontaneous resolution to form a chiral sheet structure.