Synthesis and characterization of mononuclear copper(II) and dinuclear cadmium(II) complexes with di-(2-picolyl)sulfide

Abstract

The reaction of CuCl 2 AE 2H 2 O and CdCl 2 with di-(2-picolyl)sulfide (dps) leads to the formation of mononuclear copper(II) and binuclear cadmium(II) complexes, [Cu(dps)Cl 2 ] AE H 2 O (1) and [(dps)(Cl)Cd II (l-Cl) 2 Cd II (Cl)(dps)](2). The copper atom in (1) is coordinated to one sulfur and two nitrogen atoms from the dps ligand and two chlorides in a distorted square-pyramidal environment. Complex (2) has two distorted octahedra sharing the basal edge that contain the bridging chloro ligands, each of which resides at a center of inversion. Cyclic voltammetric data show that (1) undergoes two reversible one-electron waves corresponding to Cu II /Cu III and Cu II /Cu I processes. However, cyclic voltammetry of (2) gives two irreversible reduced waves.

Staging Bonding between Group 12 Metal Ions and Neutral Selenium Donors: Intermolecular Interactions of Mixed N,Se Donor Ligands and Anions

“…The fused five-membered chelate rings in 2 have a flattened envelope conformation with the methylene carbons in the flap positions. The Cd(II) chloride complex of bis(pyridine-2-ylmethyl)­sulfane has a form isomorphic to 2 and a form crystallizing in P 2 1 / n …”

“…The Cd(II) chloride complex of bis(pyridine-2-ylmethyl)sulfane has a form isomorphic 34 to 2 and a form crystallizing in P2 1 /n. 37 The two types of dimers in 2 are stacked upon themselves down the crystallographic b axis with crystallographic inversion centers between adjacent molecules. The puckered L on the ends of each dimer have pyridyl rings nestled against a ligand associated with the other dimer such that the pyridyl rings form a crude tetrahedron (average face-edge-face angle of 65(15)°).…”