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Phanes with Three‐ and Four‐Membered Rings as Building Elements
Author(s) -
Gleiter Rolf,
Merger Martin
Publication year - 1997
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.199724261
Subject(s) - cyclobutadiene , cubane , cycloaddition , chemistry , cyclic voltammetry , stereochemistry , crystallography , metal , double bond , ion , computational chemistry , molecule , crystal structure , electrochemistry , organic chemistry , catalysis , electrode
The systematic integration of the small 2π‐ and 4π‐electron systems cyclopropenylium ion, cyclopropenone, oxo‐cyclobutenylium ion, and cyclobutadiene into phane chemistry was initiated only a few years ago. [ n 2 ]Cyclopropenylophanes, [ n 2 ]cyclopropenonophanes, metal‐capped [ n 4 ]cyclobutadienosuperphanes, and other new families of double‐decker phane species became available from cycloalkydiynes through special methods of double [2+1]cycloaddition with carbenes and metal complex induced dimerization by double [2+2]cycloaddition. Phane‐specific structural features were elucidated by X‐ray structural analyses. Cyclic voltammetry and PE spectroscopy as well as MO calculations reealed considerable interactions between closely spaced π‐electron systems. Decapping cyclobutadienosuperphanes formally extended the synthetic principle to threefold [2+2]cycloadditions resulting in [ n 4 ]‐bridged tricyclo‐[4.2.0.0 3, 5 ]octa‐3,7‐dienes, which represent a new type of cage compounds. Moreover, completion to fourfold [2+2]addition was achieved with the photoinduced transformation of [3 4 ]bridged tricyclo[4.2.0.0 3, 5 ]octa‐3,7‐diene into propella[3 4 ]cubane.