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Unimolecular Gas‐Phase Oxidation of Terminal Hydroxy Groups in [FeO(CH 2 ) n OH] + Complexes ( n = 2–8). A Case for OH Bond Activation by Late Transition‐Metal Ions. Preliminary Communication
Author(s) -
Prüsse Tilmann,
Schwarz Helmut
Publication year - 1991
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19910740815
Subject(s) - chemistry , dehydrogenation , cationic polymerization , medicinal chemistry , gas phase , alkyl , ion , metal , stereochemistry , catalysis , polymer chemistry , organic chemistry
In contrast to Fe + /diol complexes, gas‐phase dehydrogenation of the corresponding Fe II alkoxides, [FeO(CH 2 ) n CH 2 OH] + , is a highly specific process in the course of which oxidation of the terminal OH group takes place. Based on labeling studies, this is the exclusive mechanism for n = 2 and 3 ( Scheme : path ); for higher homologues, as for example [FeOf(CH 2 ) 7 CH 2 OH] + , the labeling data demonstrate that an additional mechanism is operative, involving the dehydrogenation of internal positions of the alkyl chain (path ). The Fe + ‐mediated oxidation –CH 2 OH → –CHO +H 2 : constitutes one of the rare examples of O‐H bond activation by late cationic transition‐metal ions.