Studies of synthesis, structural features of Cu(I) thiophene-2-thiocarboxylates and unprecedented desulfurization of Cu(II) thiocarboxylate complexes

Thiophene-2-thiocarboxylate complexes of Cu(I), (Ph(3)P)(2)Cu(SCOth)] (1) and H(Ph(3)P)(2)Cu(SCOth)(2)] (2) (where th = thiophene) were synthesized and characterized structurally by X-ray crystallography. Electronic absorption and emission spectral properties of the two compounds have been studied. Cu(II) complexes, (TMEDA)Cu(SCOth)(2)] (3b) and (Phen)Cu(SCOth)(2)] (4a) (where TMEDA = tetramethylethylenediamine; Phen = 1,10-phenanthroline) were prepared and characterized by spectroscopic measurements. 3b and 4a underwent desulfurization under ambient conditions readily yielding the corresponding carboxylate complexes (TMEDA)Cu(O(2)Cth)(2)] (3a) and (Phen)Cu(O(2)Cth)(2)·H(2)O] (4b). 3a and 4b have been characterized crystallographically.