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Carbenoids, nitrenoids, oxenoids: Very electrophilic „anions”︁
Author(s) -
Boche Gernot
Publication year - 1998
Publication title -
macromolecular symposia
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.257
H-Index - 76
eISSN - 1521-3900
pISSN - 1022-1360
DOI - 10.1002/masy.19981340103
Subject(s) - nucleophile , electrophile , chemistry , substitution reaction , nucleophilic substitution , substitution (logic) , group (periodic table) , metal , computational chemistry , crystallography , medicinal chemistry , stereochemistry , organic chemistry , catalysis , philosophy , linguistics
The rather interesting question why the „anionic” carbenoids 1a , nitrenoids 1b and oxenoids 1c react so easily with nucleophiles is answered by experimental investigations of their structure and by means of quantumchemical calculations. It turns out that the bond to the leaving group (C(N,O)‐X is weakened (elongated), and that the energy of the σ* C(N,O)‐X orbital is lowered. This allows for a more facile substitution of X by a nucleophile. The substitution of X − is further supported by the metal cation M + .