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Di(2‐pyridyl) Ketone Complexes of Cu I ‐ and Cu II ‐Containing Iodide and Thiocyanate Ligands: An Unusual Case of a Mixed‐Aldol Condensation
Author(s) -
Szpakolski Katherine B.,
Latham Kay,
Rix Colin J.,
White Jonathan M.
Publication year - 2010
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201000860
Subject(s) - chemistry , ketone , thiocyanate , deprotonation , iodide , copper , ligand (biochemistry) , aldol condensation , cyclohexanone , trigonal bipyramidal molecular geometry , acetone , medicinal chemistry , polymer chemistry , inorganic chemistry , crystallography , ion , catalysis , organic chemistry , crystal structure , biochemistry , receptor
Complexes containing di(2‐pyridyl) ketone ( dpk ) as a bi‐ ( N , N ) and tridentate ( N , N ,O) ligand have been synthesised1,2 and characterized by spectral and structural studies. Products 1 and 2 are polymorphs of the polymeric copper(I) complex [Cu( dpk )(NCS)] n containing dpk with thiocyanate anions which bridge to form a one‐dimensional continuous polymer chain. The novel dinuclear copper(II) complex [Cu 2 ( dpk · acetone ) 2 (NCS) 2 ] ( 3 ) was formed when 1 and 2 were allowed to stand in the supernatant. In this instance it appears that a transition‐metal‐promoted aldol condensation has occurred between the solvent acetone and the ketone carbonyl of dpk to produce the novel ligand, dpk · acetone . Product 3 contains two five‐coordinate copper(II) ions, both with trigonal bipyramidal coordination, bridged through deprotonated hydroxy groups on each dpk · acetone . A chemical rationalisation for the formation of 3 is proposed. The dinuclear copper(I) complex [Cu 2 ( dpk ) 2 I 2 ] ( 4 ) is also reported, which contains two four‐coordinate copper(I) ions that are bridged together through iodide ions.