Abstract
Binuclear copper(II) complexes bridged by oxamidate (oxd) or dithio-oxamidate (dto) groups [Cu2L2(oxd)]X2 and [Cu2L2(dto)]X2[L = 2,2′-bipyridyl (bipy) or 1,10-phenanthroline, X = NO3 or ClO4], have been synthesized. Single-crystal X-ray analysis for [Cu2(bipy)2(oxd)][ClO4]2·2dmf (dmf = dimethylformamide) reveals that the oxd2– ion in trans conformation bridges two copper(II) ions with an intermetal distance of 5.192(2)A. The configuration around each copper is square pyramidal with two nitrogens of bipy and one nitrogen and one oxygen of oxd in the basal plane and a perchlorate oxygen at the apex [2.433(9)A]. The dto-bridged complexes are characterized by two intense i.r. bands at 1 540 and 1 440 cm–1 and a charge-transfer band at (21.6–21.9)× 103 cm–1. Magnetic analyses in the temperature range 80–300 K on the basis of the Bleaney–Bowers equation gave –2J values (singlet–triplet energy separation) of 488–566 cm–1 for the oxd-bridged complexes and 726–982 cm–1 for the dto-bridged complexes, indicating that the dithio-oxamidate bridge mediates a stronger antiferromagnetic spin exchange between copper(II) ions than does the oxamidate bridge. Cyclic voltammograms for the oxd complexes show an irreversible couple at +0.1 V vs. the saturated calomel electrode which is assigned to the process CuII2→ CuICuII.
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
