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Metal Ions Control the Competition between β‐ and γ‐Hydrogen Transfer in the Generation of Propene from 1,7‐Octadiene in the Gas Phase
Author(s) -
Dange Oliver,
Steinrück Norbert,
Stöckigt Detlef,
Schwarz Helmut
Publication year - 1990
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19901230721
Subject(s) - propene , chemistry , hydrogen , hydrogen atom , metal , ion , inorganic chemistry , phase (matter) , photochemistry , catalysis , organic chemistry , alkyl
The mechanistic details (i.e. β‐versus γ‐hydrogen transfer) of transition‐metal ion induced generation of propene from metastable ion complexes of 1,7‐octadiene with M + =Cr + , Fe + , Ni + are strongly affected by the nature of M + . For Cr + the major reaction involves the transfer of an allylically activated hydrogen atom to M + (γ‐H transfer), followed by coupling of this hydrogen with the C 3 H 5 unit (Scheme 3: 8 → 9→ 11 → C 3 H 6 ). The hydrogen transfer 9→ 11 is preceded by substantial exchange reactions. A minor path for M + =Cr + corresponds to the more traditional β‐hydrogen transfer 9→ 10 . This process, however, represents the major route for propene loss induced by M + = Fe + , Ni + .