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Aza‐ versus Phospha‐Substitution in Cyclobutadiene: A Theoretical Evaluation of Bonding Properties
Author(s) -
Schoeller Wolfgang W.,
Busch Thilo
Publication year - 1993
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.199306171
Subject(s) - cyclobutadiene , isomerization , heteroatom , chemistry , computational chemistry , ab initio , fragmentation (computing) , substitution (logic) , crystallography , molecule , organic chemistry , ring (chemistry) , biology , ecology , catalysis , computer science , programming language
Completely different effects on the stability of cyclobutadiene are found upon replacement of C with N or P. Whereas in the phospha derivatives the cyclobutadiene structure is less stable than the tetrahedrane, and the barrier to valence isomerization is reduced, the exchange of N for C increases this barrier, and the tetrahedranes are prone to fragmentation. According to the results of the ab initio calculations described here, not only the monoaza‐ and monophosphacyclobutadienes but also their analogues with two heteroatoms should, in principle, be experimentally accessible.