synthesis and characterization of acyclic and cyclic azabridged ligands incorporating 2,2-bipyridine subunits and their complexes with copper(ii), cobalt(ii), and nickel(ii)合成和表征非循环和循环azabridged配体结合2,2u2019关于子单元和铜(ii)及其复合物,钴(ii)和镍(ii).pdfVIP

Molecules 2003, 8, 521-535 molecules ISSN 1420-3049 / Synthesis and Characterization of Acyclic and Cyclic Aza- bridged Ligands Incorporating 2,2-Bipyridine Subunits and Their Complexes With Copper(II), Cobalt(II), and Nickel(II) Antonino Mamo* and Andrea Pappalardo Department of Physical and Chemical Methodologies for Engineering, Engineering Faculty, University of Catania, V.le Andrea Doria 6, I-95125 Catania, Italy. Tel. (+39) 95-7382756, Fax (+39) 95-333231. * Author to whom correspondence should be addressed; e-mail: mamo@dmfci.ing.unict.it Received: 12 December 2002; in revised form: 14 June 2003 / Accepted: 16 June 2003 / Published: 15 July 2003. Abstract: The synthesis of a series of N,N-disubstituted acyclic (AL) and cyclic (CL) aza-bridged ligands incorporating 2,2-pipryidine subunits is described. 1H-NMR and IR spectral data support the proposed ligand structures. Dynamic 1H-NMR studies on diurea and diamide derivatives point to the presence of slowly interconverting conformers on the 1H-NMR time-scale, owing to N−H···N hydrogen bonding and/or a restricted rotation around the amide bonds. The ligands synthesized form 1:1 complexes with divalent transition metal ions. Upon complexation, bis-ester derivatives AL and CL undergo a 5 5 metal-induced hydrolysis of the ester groups to carboxyl functions, which act as additional