Abstract
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, typically occurring upon condensation of an amine and the unstable selenenic acid, often leading to intramolecular cyclizations, and its disruption, mainly promoted by thiols, are rather common events in organic Se-catalyzed processes. In this work, 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. The intermediate strength of the Se–N bond, which can be tuned to necessity, gives rise to significant trends when comparing it to the stronger S– and weaker Te–N bonds, reaffirming also in this context the peculiar and valuable role of selenium in chemistry and life.
Highlights
The chalcogen–nitrogen bond (X–N, X = S, Se, Te) is an important motif in chemistry and is present in many different structures, ranging from inorganic and organic materials, catalysts, protein mimics, and drugs [1,2,3,4]
The model chosen for the analysis of the chalcogen–nitrogen bonds had general formula RX–NR’2, in which X can be S, Se, or Te and R and R’ were chosen among H, CH3, and CF3
Analysis of the geometries optimized at the zeroth-order regular approximation (ZORA)-BLYP-D3(BJ)/TZ2P level of theory showed how the X–N bond length varied upon changing the chalcogen or the substituents
Summary
The chalcogen–nitrogen bond (X–N, X = S, Se, Te) is an important motif in chemistry and is present in many different structures, ranging from inorganic and organic materials, catalysts, protein mimics, and drugs [1,2,3,4]. The Se–N bond is present in the isoselenazole ring of ebselen (2-phenyl-1,2-benzisosele nazol-3(2H)-one, which is described as the first and most popular glutathione peroxidase (GPx) mimic [12,13]. This compound is endowed with antimicrobic and cytoprotective activities. The mechanistic details of its catalytic activity have not been fully elucidated [14,15,16,17,18], a nice computational investigation has provided an exhaustive picture of the possible paths [19], disclosing that the chemistry of the Se–N bond plays a crucial role in triggering the antioxidant effects [3,20]
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