Chalcogen–Nitrogen Bond: Insights into a Key Chemical Motif
Chalcogen–nitrogen chemistry deals with systems in which sulfur, selenium or tellurium is linked to a nitrogen nucleus. This chemical motif is a key component of different functional structures, ranging from inorganic materials and polymers to rationally designed catalysts, to bioinspired molecules and enzymes. The formation of a selenium–nitrogen bond, and its disruption, are rather common events in organic Se-catalyzed processes. In nature, along the mechanistic path of glutathione peroxidase, evidence of the formation of a Se–N bond in highly oxidizing conditions has been reported and interpreted as a strategy to protect the selenoenzyme from overoxidation. Selenium is also bonded to nitrogen in the well-known ebselen, a selenenylamide with antioxidant, antimicrobic and cytoprotective activity and its formation/disruption has a crucial role for its pharmacological action. Focusing on examples taken from selenium organic chemistry and biochemistry, the selenium–nitrogen bond is described, and its strength and reactivity are quantified using accurate computational methods applied to model molecular systems. Significant trends show up when comparing to sulfur/tellurium–nitrogen bonds, also reaffirming the peculiar and valuable role of selenium in chemistry and life in this context.