Abstract
Five new heteroleptic complexes of Cu(I), Ag(I), and Ni(II) having formulae [Cu-3(dtc)(2)(dppf)(2)]PF6(Cu-I), [Cu-3(dtc)(2)(dppe)(2)]PF6(Cu-II), [Cu(PPh3)(2)(dtc)] (Cu-III), [Ag-3(dtc)(2)(PPh3)(2)]NO3(Ag-I), and [Ni(dtc)(dppf)]PF6(Ni-I) (dtc =N-ethanol-N-methylferrocenyl-dithiocarbamate; dppf = 1,1 '-bis(diphenylphosphino)ferrocene; dppe = 1,1 '-bis(diphenylphosphino)ethane; PPh3= tripheylphosphine) have been synthesized and characterized using elemental analysis, Fourier-transform infrared, multinuclear nuclear magnetic resonance, UV-Vis spectroscopy, and single-crystal X-ray diffraction. The single-crystal X-ray diffraction studies indicate thatAg-Iforms a rare trinuclear cluster in which the geometry around the two silver centers Ag1 and Ag3 is distorted tetrahedral, whereas the third silver center Ag2 shows a distorted trigonal planar geometry. TheNi-Icomplex has a distorted square-planar geometry around the Ni center. In addition, a side product [Ag-2{S-2(dppf)(2)}] (Ag-II) was obtained during an attempt to synthesize [Ag(dppf)(dtc)], where the two Ag centers are bridged by two sulfido centers and coordinated with two phosphorus centers of the dppf ligand to give rise to a distorted tetrahedral geometry. The solid-state structures ofAg-I,Ni-I, andAg-IIare stabilized by a variety of weak interactions. The nature of these interactions has been addressed with the help of Hirshfeld surface analyses. In addition, the weak argentophilic interaction inAg-IandAg-IIhave been studied using quantum theory of atoms in molecules and natural bond orbital calculations. The electrochemical properties of the complexes have been investigated using cyclic voltammetry, whereCu-IandCu-IIexhibited two quasi-reversible waves, whereasCu-III,Ag-I,Ag-II, andNi-Iexhibited only one quasi-reversible peak.