Highly Electrophilic, Catalytically Active and Redox-Responsive Cobaltoceniumyl and Ferrocenyl Triazolylidene Coinage Metal Complexes.

A convenient access to a triad of triazoles with ferrocenyl and cobaltoceniumyl substituents is reported. N-Alkylation, deprotonation and metalation with CuI /AgI /AuI synthons affords the heteroleptic triazolylidene complexes. Due to the combination of neutral, electron-donating ferrocenyl substituents and cationic, strongly electron-withdrawing cobaltocenium substituents, the mesoionic carbene (MIC) ligands of these complexes are electronically interesting "push-pull", "pull-push" and "pull-pull" metalloligands with further switchable redox states based on their fully reversible FeII /FeIII , (ferrocene/ferrocenium) and CoIII /CoII , (cobaltocenium/cobaltocene) redox couples. These are the first examples of metal complexes of (di)cationic NHC ligands based on cobaltoceniumyl substituents. DFT calculated Tolman electronic parameter (TEP) of the new MIC ligands, show these metalloligands to be extremely electron-poor NHCs with properties unmatched in other carbene chemistry. Utilization of these multimetallic electronically tunable compounds in catalytic oxazoline synthesis and in antitumor studies are presented. Remarkably, 1 mol % of the AuI complex with the dicationic MIC ligand displays full catalytic conversion, without the need for any other additives, in less than 2 hours at ambient temperatures. These results thus firmly establish these new classes of cobaltoceniumyl based (di)cationic MIC ligands as prominent players in several branches of chemistry.

Upcycling of cotton polyester blended textile waste to new man-made cellulose fibers.

The creation of a circular economy for cellulose based textile waste is supported by the development of an upcycling method for cotton polyester blended waste garments. We present a separation procedure for cotton and polyester using [DBNH] [OAc], a superbase based ionic liquid, which allows the selective dissolution of the cellulose component. After the removal of PET, the resulting solution could be employed to dry-jet wet spin textile grade cellulose fibers down to the microfiber range (0.75-2.95 dtex) with breaking tenacities (27-48 cN/tex) and elongations (7-9%) comparable to commercial Lyocell fibers made from high-purity dissolving pulp. The treatment time in [DBNH] [OAc] was found to reduce the tensile properties (<52%) and the molar mass distribution (<51%) of PET under certain processing conditions.

Solid-state NMR method for the quantification of cellulose and polyester in textile blends.

The valorization of cellulose rich textile waste is promoted by the development of a novel solid-state NMR method for the quantification of cellulose and polyester in textile blends. We applied 13C CP-MAS NMR as a tool for the quantification and structural characterization of cellulose in cotton polyester blends. Gaussian functions were used to integrate the spectra obtained from a set of calibration standards in order to calculate a sigmoidal calibration curve. Acid hydrolysis was chosen as a reference method. The results demonstrated that solid-state NMR enables a reliable determination of cellulose and polyester in both preconsumer and postconsumer waste textiles and suggests a possible extension of the concept to blends of man-made cellulose fibers (MMCFs) and polyester.

Crystal structure of 1-(1-methyl-1H-imidazol-2-yl)-4-phenyl-1H-1,2,3-triazole dihydrate.

The title compound, C12H11N5·2H2O, which crystallizes as a dihydrate, was obtained by Cu(I)-catalysed azide-alkyne cyclo-addition from 2-azido-1-methyl-imidazole and phenyl-ethyne. The dihedral angles between the central triazole ring (r.m.s. deviation = 0.004 Å) and the pendant imidazole (r.m.s. deviation = 0.006 Å) and phenyl rings are 12.3 (2) and 2.54 (19)°, respectively. In the crystal, the water mol-ecules are connected into [010] chains by O-H⋯O hydrogen bonds, while O-H⋯N hydrogen bonds connect the water mol-ecules to the organic mol-ecules, generating corrugated (100) sheets.