STEREOCHEMISTRY OF INCIPIENT ELECTROPHILIC AND NUCLEOPHILIC REACTIONS AT DIVALENT SELENIUM CENTER: ELECTROPHILIC-NUCLEOPHILIC PAIRING AND ANISOTROPIC SHAPE OF Se IN Se…Se INTERACTIONS

Abstract

Using the Cambridge Crystallographic Data Base and computer retrieval methods, we have studied the preferred directions of approach of nucleophiles and electrophiles at divalent selenium centers. We find that electrophiles approach Se in a direction nearly normal to the selenide plane Y-Se-Z while nucleophiles approach Se nearly in the selenide plane and along the back side of Y-Se or Z-Se bonds. We also found evidence for the incipient formation of attractive electrophile-nucleophile pairing in Se…Se interactions. Other Se…Se contacts which did not fit the above pattern showed non-spherical effective shape for Se atoms. The preferred directions of approach of electrophiles and nucleophiles for Se and S are very similar and may be understood in terms of frontier orbitals. Such similarity in the shape and orbital environment of S and Se indicate to some extent how Se can play the role of S in some enzymes.