Interaction of an extended series of N-substituted di(2-picolyl)amine derivatives with copper(II). Synthetic, structural, magnetic and solution studies.
The interaction of Cu(II) with the following secondary N-substituted derivatives of di(2-picolyl)amine () are reported: N-cyclohexylmethyl-di(2-picolyl)amine (), N-benzyl-di(2-picolyl)amine (), N-(4-pyridylmethyl)-di(2-picolyl)amine (), N-(4-carboxymethylbenzyl)-di(2-picolyl)amine (), N-(9-anthracen-8-ylmethyl)-di(2-picolyl)amine (), 1,3-bis[di(2-picolyl)aminomethyl]benzene (), 1,4-bis[di(2-picolyl)aminomethyl]benzene () and 2,4,6-tris[di(2-picolyl)amino]triazine (). The solid complexes [Cu()(micro-Cl)](2)(PF(6))(2), [Cu()(micro-Cl)](2)(PF(6))(2).0.5CH(2)Cl(2), Cu()(ClO(4))(2), Cu()(2)(ClO(4))(2), [Cu()(ClO(4))(2)(H(2)O)].0.5H(2)O, Cu(2)()(ClO(4))(4), [Cu(2)()(Cl)(4)] and [Cu(2)(+H)(micro-OCH(3))(2)(H(2)O)](ClO(4))(3).C(4)H(10)O were isolated and X-ray structures of [Cu()(micro-Cl)](2)(PF(6))(2), [Cu()(micro-Cl)](2)(PF(6))(2).0.5CH(2)Cl(2,) [Cu()(2)(ClO(4))(2)(H(2)O)].0.5H(2)O, [Cu(2)()Cl(4)] and [Cu(2)(+H)(micro-OCH(3))(2)(H(2)O)](ClO(4))(3).C(4)H(10)O were obtained. The series is characterised by a varied range of coordination geometries and lattice architectures which in the case of [Cu()(ClO(4))(2)(H(2)O)].0.5H(2)O includes a chain-like structure formed by unusual intermolecular pi-interactions between metal bound perchlorate anions and the aromatic rings of adjacent anthracenyl groups. Variable temperature magnetic susceptibility measurements have been performed for [Cu()(micro-Cl)](2)(PF(6))(2) and [Cu()(micro-Cl)](2)(PF(6))(2).0.5H(2)O over the range 2-300 K. Both compounds show Curie-Weiss behaviour, with the data indicating weak antiferromagnetic interaction between the pairs of copper ions in each complex. Liquid-liquid (H(2)O/CHCl(3)) extraction experiments involving and as extractants showed that, relative to the parent (unsubstituted) dipic ligand , substitution at the secondary amine site in each case resulted in an increase in extraction efficiency towards Cu(II) (as its perchlorate salt); at least in part, this increase may be attributed to the enhanced lipophilicities of the N-substituted derivatives.
Antonioli
Bianca
B
Department of Chemistry and Food Chemistry, Technical University Dresden, 01062, Dresden, Germany.
Büchner
Bernd
B
Clegg
Jack K
JK
Gloe
Kerstin
K
Gloe
Karsten
K
Götzke
Linda
L
Heine
Axel
A
Jäger
Anne
A
Jolliffe
Katrina A
KA
Kataeva
Olga
O
Kataev
Vladislav
V
Klingeler
Rüdiger
R
Krause
Tilo
T
Lindoy
Leonard F
LF
Popa
Andreia
A
Seichter
Wilhelm
W
Wenzel
Marco
M
D000588:Amines / Q000737:chemistry*; D016880:Anisotropy; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D004578:Electron Spin Resonance Spectroscopy; D006571:Heterocyclic Compounds / Q000138:chemical synthesis / Q000737:chemistry; D008280:Magnetics; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010848:Picolinic Acids / Q000737:chemistry*; D012997:Solvents / Q000737:chemistry
C501847:2,2'-dipicolylamine; D000588:Amines; D006571:Heterocyclic Compounds; D009942:Organometallic Compounds; D010848:Picolinic Acids; D012997:Solvents; D003300:Copper