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Strained hydrocarbons from cyclic diynes—preparation and reactivity
Author(s) -
Bethke Sabine,
Brand Stefan,
Treptow Björn,
Gleiter Rolf
Publication year - 2002
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.500
Subject(s) - thermochemistry , chemistry , hydrocarbon , quantum chemical , benzene , diene , reactivity (psychology) , computational chemistry , photochemistry , standard enthalpy of formation , medicinal chemistry , organic chemistry , molecule , medicine , natural rubber , alternative medicine , pathology
The reaction of cyclic diynes with either CpCo(CO) 2 or AlCl 3 yielded strained hydrocarbons in which a Dewar benzene or a tricyclo[4.2.0.0 2,5 ]octa‐3,7‐diene frame is bridged by hydrocarbon chains. The photochemistry and thermochemistry of these species are discussed. Results of quantum chemical calculations (DFT, CASPT2) are used to discuss the thermochemistry of four different fourfold bridged tricyclo[4.2.0.0 2,5 ]octa‐3,7‐dienes. Depending on the bridging mode, either a Cope‐type rearrangement or a ring opening reaction is preferred. Copyright © 2002 John Wiley & Sons, Ltd.