10.1023/A:1015037008399
The study discusses a novel approach to replacing carbonyl ligands in cobalt clusters through the oxidation of an electroactive organometallic group linked to the cluster fragment via a conducting chain. The researchers used compounds with the electroactive group Cp*(dppe)Fe, which is connected to a Co2C2-type cluster by an acetylenide bridge. The purpose of these chemicals was to demonstrate the potential of this method as a model for molecular devices with a switch-on (oxidation) and switch-off (reduction) mechanism. The study involved the oxidation of compound I with Cp2FeBF4 to produce labile radical cations, which upon the addition of diphenylphosphinomethane (dppm), led to the replacement of carbonyl ligands and the formation of stable radical cations [2a,b]+. These cations were then reduced with Cp2Co to yield neutral diamagnetic compounds. The chemicals used served to facilitate these transformations and to characterize the resulting complexes through elemental analysis, IR spectroscopy, and NMR spectroscopy.
10.1016/j.jorganchem.2015.12.005
The study focuses on the synthesis, characterization, and kinetic investigation of a cycloplatinated(II) complex bearing 2-vinylpyridine and monodentate phosphine ligands. The main chemical used was the 2-vinylpyridinate complex [PtMe(Vpy)(DMSO)], denoted as complex C, which was prepared from the dimeric platinum(II) complex cis,cis-[Me2Pt(m-SMe2)2PtMe2], known as complex B, in the presence of DMSO (dimethyl sulfoxide) and 2-vinylpyridine ligand. The DMSO molecule in complex C was substituted by methyldiphenylphosphine (PPh2Me) to synthesize [PtMe(Vpy)(PPh2Me)], referred to as complex 1. This complex was characterized by its optical properties, showing intense phosphorescence emission in solid state and solution, and was attributed to a mixed 3ILCT/3MLCT excited state. The study also investigated the oxidative addition reaction of complex 1 with alkyl halide (MeI), resulting in the formation of [PtMe2I(Vpy)(PPh2Me)], known as complex 2. Kinetic studies suggested that this reaction proceeded via a classical SN2 mechanism, and the rate of the reaction at different temperatures was measured, yielding a high negative DS# value that supported the proposed mechanism. The study serves to understand the reactivity of cycloplatinated complexes and their potential applications in fields such as optoelectronics and medicinal chemistry.