Ru^II and Ru^III Chloronitrile Complexes: Synthesis, Reaction Chemistry, Solid State Structure, and (Spectro)Electrochemical Behavior

Abstract

The synthesis of [Ti 6 O 4 (OiPr) 8 (O 2 CPh) 8 ] (3) and [RuCl(NϵCR) 5 ][RuCl 4 (NϵCR) 2 ] (4a, R = Me; 4b, R = Ph), [Ru(NϵCPh) 6 ][RuCl 4 (NϵCPh) 2 ] (5) and [H 3 O][RuCl 4 (NϵCMe) 2 ] (7a) is discussed. Crystallization of 5 from CH 2 Cl 2 gave trans-[RuCl 2 (NϵCPh) 4 ] (6). The solid-state structures of 3, 4a,b, 5, 6 and 7a are reported. Complex 4b forms a 3D network, while 6 displays a 2D structure, due to π-interactions between the benzonitrile ligands. The (spectro)electrochemical behavior of 4a,b and 6 was studied at 25 and-72°C and the results thereof are compared with [NEt 4 ]

S-Scheme Bi-oxide/Ti-oxide Molecular Hybrid for Photocatalytic Cycloaddition of Carbon Dioxide to Epoxides

“…Next, in the absence of TBAB, no conversion occurred, indicating that it could not be avoided (entry 5). To the best of our knowledge, ammonium or other nitrogen-containing halide salts were always essential for activation of epoxides in CO 2 insertion in previous reports using Lewis acid catalysts or photocatalysts. − We also studied the activities of the undoped Ti-oxide carboxylates including Ti 6 O 6 Bz 6 (O i Pr) 6 and Ti 8 O 8 Bz 16 and the commercial TiO 2 P25. However, their activities were much lower than that of Ti 18 Bi 4 (entries 6–8).…”

Ferrocenyl-based di- and trinuclear lanthanide complexes: solid state structures, (spectro)electrochemical and DFT studies

“…75,76 Ferrocene itself showed a redox potential of 220 mV vs. Ag/Ag + (ΔE p = 61 mV) within the measurements. 77 UV-Vis/NIR studies were carried out in an OTTLE (= Optically Transparent Thin-Layer Electrochemical) cell with quartz windows similar to that described previously, 78 in anhydrous dichloromethane solutions containing 5.0 mmol L −1 of the analyte and 0.1 mol L −1 of [Bu 4 N][B(C 6 F 5 ) 4 ] as supporting electrolyte using a Varian Cary 5000 spectrophotometer at 25 °C. The working electrode Pt-mesh, the AgCl-coated Ag wire for reference and the Pt-mesh auxiliary electrode are meltsealed into a polyethylene foil.…”