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Chemistry of α‐Ketoacyl Metal Complexes
Author(s) -
Chen JwuTing
Publication year - 1992
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.199200094
Subject(s) - chemistry , aryl , stereochemistry , decarbonylation , carbonylation , cyclopentane , reductive elimination , metal , medicinal chemistry , alkyl , catalysis , organic chemistry , carbon monoxide
The α‐ketoacyl complexes constitute a new family of organometallic compounds. The α‐ketoacyl ligands have a strong influence and generally follow a decreasing order of acyl > α‐ketoacyl > alkyl or aryl. The oxalyl conformation exhibits planar s‐cis, perpendicular and planar s ‐trans structures. In comparison with the standard C ( sp 2 ) ‐C ( sp 2 ) bond, the oxalyl C‐C bonds of the α‐ketoacyl ligands are relatively long, indicating that the electronic derealization between the oxalyl carbonyls are of the least importance. The weak C‐C bond between the α‐ketoacyl carbonyls affords a driving force of the decarbonylative reactivity of such ligands; it is also responsible for the difficulty of formation of the α‐ketoacyl complex via insertion of CO into the metal‐acyl bond. However, α‐ketoacyl complexes can be kinetically stable. Kinetic studies of decarbonylation of the α‐ketoacyl complexes provided a profound understanding of the mechanism of novel catalytic reactions of double carbonylation. The α‐ketoacyl complexes show promise to explore rare acyl migration and the reductive coupling of C( sp 2 )‐C( sp 2 ) bonds in a fundamental way.