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Tris(3,4‐dimethylenecyclobuteno)benzene Derivatives with Enhanced Carbon–Carbon Bond‐Length Alternation in Annelated Benzene
Author(s) -
Hou Kaipeng,
Wang Chenli,
Zhou Yunfei,
Abosede Ogunlana,
Bao Xiaoguang
Publication year - 2016
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201600731
Subject(s) - chemistry , benzene , heteroatom , moiety , ring (chemistry) , molecule , carbon fibers , bond length , crystallography , stereochemistry , medicinal chemistry , organic chemistry , composite number , materials science , composite material
Computational analyses of the tris(3,4‐dimethylenecyclobuteno)benzene molecule indicate that the absence of the equivalent of a HOMO of an etheno group between the internal carbon atoms of the annelating butadieno groups is mainly responsible for the relatively weak cyclohexatriene‐like fixation in the central benzene ring. To increase the extent of C–C bond‐length alternation in the benzene moiety, two strategies of modification of the annelating groups are proposed to make the presence of the equivalent of a HOMO of an etheno group between the internal carbon atoms of the annelating butadieno groups. The first is to introduce a π‐electron‐donating heteroatom/group to form a five‐membered ring with the annelating butadieno groups (model I ). The extent of bond‐length alternation could be tuned by the choice of the heteroatom/group in model I . The second is to coordinate with transition‐metal groups, such as the irontricarbonyl groups, for the annelating butadieno groups (model II ). Computational results predict that molecules generated by using these two strategies could form strong cyclohexatriene‐like fixation of the double bonds in the central benzene ring.