Multifrequency EPR and Redox Reactivity Investigations of a Bis(μ-thiolato)-dicopper(II,II) Complex.

{From a new tripodal ligand [N2SS'H], (o-HSC6H4CH2)(o-tBuC6H4CH2)NCHC6H5, with mixed N,S(thioether), and S(thiolate) donor set, [Cu2(N2SS')2](ClO4)2.Et2O (1) was prepd. and characterized. X-ray crystallog. anal. of 1 demonstrates that the two five-coordinated Cu atoms are bridged by two thiolates leading to a nearly planar Cu2S2 core with a Cu1···Cu1* distance of 3.418(8) {\AA} and a large bridging angle Cu1S1Cu1* of 94.92°. X-band (10 GHz), Q-band (34 GHz), and F-Band (115 GHz) EPR spectra of 1 are consistent with a weakly coupled dicopper(II,II) center attributed to an S = 1 state. Simulations for the three frequencies were obtained with a unique set of electronic parameters. The mean values of the spin Hamiltonian parameters for 1 are |D| = 0.210(3) cm-1


Soumis le 12 avril 2018