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Cycloalkadiynes—From Bent Triple Bonds to Strained Cage Compounds
Author(s) -
Gleiter Rolf
Publication year - 1992
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.199200271
Subject(s) - diacetylene , cyclobutadiene , chemistry , cyclopentadienyl complex , intramolecular force , triple bond , ring (chemistry) , crystallography , bent molecular geometry , intermolecular force , stereochemistry , polymer chemistry , double bond , organic chemistry , catalysis , molecule , polymerization , polymer
The synthesis of Cycloalkadiynes with medium‐sized rings may be accomplished by a number of ring‐closing and elimination reactions. Information concerning the conformation of the rings as well as the extent of transannular interaction between the triple bonds is obtained by analysis of X‐ray crystallographic data and by photoelectron spectroscopy. The diacetylene complexes of Ag 1 and Cu 1 show hardly any structural change compared to the uncomplexed compounds while the bis(hexacarbonyldicobalt) complexes differ significantly in their structural parameters. Reaction of Cycloalkadiynes with dicarbonyl(η 5 ‐cyclopentadienyl)cobalt yields inter‐ and intramolecular cyclobutadiene complexes. The superphane of cyclobutadiene formed by the intermolecular reaction can be transformed into a number of highly strained cage compounds in few steps. In addition, the variety of such cage compounds can be increased if the reaction of a cyclic diacetylene is carried out with dimethylacetylenedicarboxylate in the presence of aluminum chloride. The intermediate bridged Dewar benzenes eventually lead to propellaprismanes.