Ubiquity of cubanes in bioinorganic relevant compounds.

• Review of the history of heterocubane clusters. • Connections between biological and synthetic systems. • Connections between bioinorganic cubanes and older synthetic systems or other synthetic systems not previously connected to biology. • Discussion of electronic structure, spectroscopic, and computational aspects. The heterocubane (commonly referred to as the cubane cluster, a molecular species comprising a cube-shaped core with different atom types at opposite corners) is a conserved general structure found in some of nature's most crucial enzymes. Nature owes some of its most important reactions—like catalytic water splitting, nitrogen fixation, and the citric acid cycle—to the reactive versatility of the cubane structure. Few reviews have comprehensively highlighted the importance of this naturally occurring structure outside of (and prior to) the biological context, or have explicitly focused on the role of the cluster's global coordination environment on reactivity and electronic structure across multiple core metal and core ligand identities. In this review we summarize the scope of existing synthetic chemistry in context of coordination environment and geometry. Connections are drawn between these systems and the natural systems to offer insights into the properties of heterocubane clusters and their relation to biology. With biological uses ranging from simple one-electron transfer to some of the most challenging chemistries such as water oxidation and nitrogen fixation, the cubane cluster is ubiquitous and requires a more general elaboration than has been previously provided; thus, we aim to provide a summary of the history and the current research climate regarding heterocubanes, hoping that it will inspire future endeavors and discoveries. [ABSTRACT FROM AUTHOR]