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Carbon–oxygen bond cleavage in allylic esters promoted by low‐valent transition‐metal hydride complexes
Author(s) -
Srivastava R S
Publication year - 1993
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/aoc.590070803
Subject(s) - chemistry , allylic rearrangement , hydride , cleavage (geology) , bond cleavage , medicinal chemistry , ruthenium , rhodium , transition metal , stereochemistry , oxygen , metal , carbon fibers , catalysis , organic chemistry , materials science , geotechnical engineering , fracture (geology) , composite number , composite material , engineering
CoH(N 2 )(PPh 3 ) 3 promotes carbon–oxygen (CO) bond cleavage in allylic carboxylates to give the corresponding olefins at room temperature. On the other hand, RuH 2 (PPh 3 ) 4 and RhH(PPh 3 ) 4 are mainly active for CO bond cleavage at elevated temperature. Reaction proceeds through a mechanism involving predissociation of one of the tertiary phosphines from the RuH 2 (PPh 3 ) 4 and RhH(PPh 3 ) 4 and competitive coordination of allylic carboxylates and PPh 3 to the vacant site on ruthenium and rhodium. A new six‐membered metallocyclic complex, Co(OCOCH 2 COCH 3 )(PPh 3 ) 2 , has been isolated.