Molecular catalyst systems as key enablers for tailored polyesters and polycarbonate recycling concepts.

A transition metal catalyst system for the selective catalytic depolymerization of various polyester- and polycarbonate-based materials is presented. The use of a molecular ruthenium catalyst with selected triphos ligands enabled a selective hydrogenolysis of a large diversity of polymeric consumer products, paving the way to innovative and sustainable recycling strategies within a circular economy.

Assessing the Intracellular Integrity of Phosphine-Stabilized Ultrasmall Cytotoxic Gold Nanoparticles Enabled by Fluorescence Labeling.

As the size of nanoparticles (NPs) is in the range of biological molecules and subcellular structures, they provide new perspectives in biomedicine. This work presents studies concerning the cellular uptake and distribution of phosphine-stabilized cytotoxic 1.4 nm sized AuNPs and their probable degradation during this process. Therefore, ultrasmall phosphine-stabilized AuNPs are modified by linking a fluorophore covalently to the ligand shell. Monitoring the fluorescence on a cellular level by means of flow cytometry and confocal laser scanning microscopy allows determining the fate of the ligand shell during AuNP cell internalization, due to the fact that the fluorescence of a fluorophore bound near to the AuNP surface is quenched. Cell fractionation is conducted in order to quantify the AuNP content at the cell membrane, in the cytoplasm, and the cell nucleus. The incubation of cells with the fluorophore-modified AuNPs reveals a partial loss of the ligand shell upon AuNP cell interaction, evident by the emerging fluorescence signal. This loss is the precondition to unfold high AuNP cytotoxicity. Together with their significantly different biodistribution and enhanced circulation times compared to larger AuNPs, the findings demonstrate the high potential of ultrasmall AuNPs for drug development or therapy.

Ruthenium-Catalyzed Modular Synthesis of Cyclic Tertiary Amines from Lactams.

Reported is the development of a novel catalytic cascade reaction facilitating the modular synthesis of cyclic tertiary amines from simple lactam substrates and secondary alcohols. Using a single molecular ruthenium-triphos catalyst in the presence of molecular hydrogen enabled the versatile formation of various amines in high yield with excellent selectivity. Extending the reaction system to using an alcohol as the hydrogen transfer reagent allowed the reduction of lactams without the need for molecular hydrogen.

Synthesis of a sterically bulky diphosphine synthon and Ru(ii) complexes of a cooperative tridentate enamide-diphosphine ligand platform.

In order to generate tridentate enamido diphosphine ligand platforms, we developed procedures for the preparation of tBu2PCH2CH2P(tBu)I, which involve low temperatures, pentane solvent and addition of 4 equiv. of tBuLi to Cl2PCH2CH2PCl2 or 2 equiv. of tBuLi to known Cl(tBu)PCH2CH2P(tBu)Cl also at low temperatures in pentane; an alternate method involves the inverse addition of Cl(tBu)PCH2CH2P(tBu)Cl to 2 equiv. of tBuLi in pentane at 0 °C; all of these methods generate good yields of the tetraphosphine dimer (tBu2PCH2CH2P(tBu))2 contaminated by small amounts of tBu2PCH2CH2PtBu2 (dtbpe), which can be conveniently separated by sublimation. Subsequent oxidative cleavage of the P-P bond with I2 or 1,2-diiodoethane results in the formation of the desired tBu2PCH2CH2P(tBu)I, which undergoes C-P bond formation when added to 1 equiv. of the lithium N-2,6-diisopropylphenylenamide of cyclopentylidene imine to generate the HNPP ligand precursor; this species exists as a tautomeric mixture of the corresponding enamine and imine, the ratio of which depends on workup conditions used. This enamine-imine mixture can be used directly to form Ru(ii) species either directly with heating to generate the five-coordinate (NPP)RuCl(CO) via loss of H2 or by inclusion of 1 equiv. of KOtBu to generate (NPP)RuH(CO). X-ray crystallographic studies confirm that the geometry in the solid state matches the solution spectroscopic data. Subsequent studies of (NPP)RuH(CO) indicate that it reacts with benzaldehyde, benzyl alcohol, and H2 in a cooperative manner to generate a series of hydride carbonyls that have been characterized fully by NMR spectroscopy and X-ray crystallography.

Tailor-Made Ruthenium-Triphos Catalysts for the Selective Homogeneous Hydrogenation of Lactams.

The development of a tailored tridentate ligand enabled the synthesis of a molecular ruthenium-triphos catalyst, eliminating dimerization as the major deactivation pathway. The novel catalyst design showed strongly increased performance and facilitated the hydrogenation of highly challenging lactam substrates with unprecedented activity and selectivity.