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Fe + ‐Mediated Dehydrogenation of 2‐Propanol and Ethanol by 1,3‐Butadiene and Evidence for Interligand Hydrogen Exchange Processes
Author(s) -
Karraß Sigurd,
Schröder Detlef,
Schwarz Helmut
Publication year - 1992
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.19921250331
Subject(s) - chemistry , dehydrogenation , isotopomers , hydrogen , propanol , catalysis , alkene , hydrogen atom , ligand (biochemistry) , hydride , ethanol , medicinal chemistry , alcohol , photochemistry , methanol , inorganic chemistry , organic chemistry , molecule , alkyl , biochemistry , receptor
Gas‐phase experiments on the Fe + ‐mediated oxidation of 2‐propanol and ethanol by 1,3‐butadiene are described. The reaction takes place at an atomic Fe + centre, and labeling experiments uncover its specificity. While the gas‐phase reaction of Fe(η 4 ‐C 4 H 6 ) + with 2‐propanol occurs at collision‐rate and the analysis of ligand‐binding energies, in principle, favour a catalytic cycle for the Fe + ‐mediated dehydrogenation of 2‐propanol by 1,3‐butadiene, this conjecture is not born out experimentally due to complicating “side” processes. In addition to the specific interligand two‐hydrogen‐atom transfer from the alcohol to butadiene, the study of isotopomers reveals several hydrogen‐exchange processes preceding dehydrogenation, dehydration, and alkene loss from (C 4 H 6 )Fe + (alcohol) complexes.