Catalytic Chemistry of Homogeneous Platinum Group Metal Complexes

Dear Colleagues,

During the last 20 years, the prices of precious metals have risen to about 5-fold due to limited resources and economic crises. Among these, the most efficient and most frequently used catalyst metals, palladium (Pd) and rhodium (Rh), have correlated least to gold (Au) due to very high fluctuation in demand and supply. For example, the price of Pd and Rh peaked at 97,000 $/kg and 405,000 $/kg, respectively, earlier this year. However, the average price level of the catalyst cost of Rh, Pd, Os, Ir, and Pt (except perhaps Ru) can constitute a serious strain in the profitability of even small-scale fine chemicals. Therefore, research has focused on the exploitation of the highest selectivity, activity, and stability from the complexes of the Pt group in homogeneous catalysis. For this goal, the mechanism and kinetics of these catalytic reactions have been investigated very extensively, including the appropriate elementary steps, such as oxidative additions, migratory insertions, reductive eliminations, metallacycle formations, nucleophile attacks on metal–organic bonds, etc. Other important aspects, such as the influences of the cone-angles, the bite-angles, and the electronic and the steric properties of both the ligands and the anions, have also been thoroughly investigated. Furthermore, ample effort has been made to improve the durability and the practical recyclability of these catalyst complexes, especially by industrial research groups. By the use of other, relatively cheap members of late transition metal complexes as a catalyst, some of the issues above are also important, but the main interest in this case is to replace the expensive platinum group catalysts. Although the latter is a very sensible goal, the challenges and tasks involved in it are different. Thus, the present Special Issue intents to cover the recent progresses and trends in platinum group metals as expensive members of late transition metal catalysts only. Specifically, the aim and scope of this Special Issue is to describe any new or undisclosed measures or an improved catalytic reaction procedure or step, which help to enhance selectivity and stability beyond present limits in homogeneous catalytic reactions of the complexes of the Pt group. Spectroscopic and kinetic studies on the mechanisms, which disclose intrinsic problems associated with certain ligands and anions are especially sought. Elucidations and preventions of the deactivation paths of the catalysts, such as dimer (cluster) formations, quaternizations of P- or N-ligands, oxidation, and other ligand degradation paths leading to metal plating are also highly valued. Naturally, any new catalytic reaction or an efficiently modified new variant of an existing reaction would also be welcome using these homogeneous catalysts.

Dr. Imre Tóth
Guest Editor

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• Complexes of the Pt Group Metals (Ru, Rh, Pd, Os, Ir and Pt)
• In situ or online (NMR, IR, UV) spectroscopic studies
• Kinetic studies
• Separate DFT and NMR studies on the vital catalytic steps
• Formation and regeneration of the catalytically active species
• Optimizing the parameters of the ligand for catalysis
• Role of the anions in the catalysis
• Intrinsic problems with some ligand/anion choices
• Facilitation of the rate determining catalytic steps
• Prevention of metal plating