Understanding structure and reactivity of new fundamental inorganic molecules: metal sulfides, metallocarbohedrenes, and nitrogenase

A large number of new and unexpected molecules, fundamentally inorganic and containing just metal and sulfur, or metal and carbon, can be synthesised in the gas phase, and their reactivities investigated, In the absence of bulk samples and definitive characterisation data they can be very profitably investigated using density functional calculations. A valuable perspective places these new and unprotected molecules in the context of related nonmolecular solids, and terminally ligated molecules. The Fe7MoS9 cluster which effects the mild reduction of N-2 at the active site of nitrogenase is similarly undercoordinated, floppy, and reactive. Density functional calculations reveal the characteristics of the Fe Fe7MoS9 site and elucidate postulated mechanisms for the reduction.