Synthesis of molybdenum(vi) dioxido complexes 1-3, coordinated by one or two functionalized iminophenolate ligands HL1 or HL2, bearing a donor atom side chain or a phenyl substituent, respectively, allowed for systematic investigation of the oxygen atom transfer (OAT) reactivity of such complexes towards phosphanes. Depending on stoichiometry and employed phosphane (PMe3 or PPh3), different molybdenum(iv) and molybdenum(v) complexes 4-7 were obtained. Whereas molybdenum(iv) complexes 4 and 5, bearing a terminal PMe3 ligand, readily reacted with molecular O2 to form oxido peroxido complexes 8 and 9, phosphane free μ-oxido bridged dinuclear molybdenum(v) complexes 6 and 7 proved to be stable towards oxidation with molecular O2 under ambient conditions. Single-crystal X-ray diffraction analyses revealed different isomeric structures in the solid state for dioxido complexes 1 and 2 in comparison with oxido phosphane complex 5, dinuclear oxido μ-oxido complex 6 and oxido peroxido complexes 8 and 9, pointing towards an isomeric rearrangement during OAT. Compounds 1 and 2 were furthermore tested for their ability to catalyze the aerobic oxidation of PMe3 and PPh3. A significant difference in catalytic activity has been observed in the oxidation of PMe3, where complex 1 bearing donor atom functionalized ligands led to higher conversion and selectivity than complex 2 coordinated by phenyl iminophenolate ligands. In the oxidation of PPh3, complex 2 leads to higher conversion compared to 1. In a control experiment, phenyl-based dinuclear μ-oxido complex 7, derived from complex 2, was found to be catalytically active, which suggests a lower energy barrier for disproportionation into [MoO(L)2] and [MoO2(L)2] in comparison with methoxypropylene based compound 6, a prerequisite for subsequent reactivity toward molecular O2.

Elastomer-based 3D objects with good resolution are fabricated by additive manufacturing of photo-reactive liquid rubber formulations with digital light processing.

Organic rubbers, comprising carbon-carbon links in their polymer backbone, are an essential part of modern everyday life. Tough, their unique properties are mainly governed by reinforcing fillers such as carbon black and silica. However, the reinforcing power is not only driven by the chemical nature of fillers but also by their particle size, shape, distribution and dispersion. In order to minimize agglomeration and processing difficulties, the idea of in situ generated fillers has been approached. In situ means "locally" and refers to the generation of fillers during the vulcanization process. This versatile technique provides individual tailoring of rubber compounds due to numerous possible reaction pathways. In situ reinforcement has been reported for all relevant rubber matrixes and is already employed commercially. In this review, a comprehensive overview of possible in situ reinforcing strategies for organic rubbers and their impact on mechanical properties is provided. It covers the reinforcing power of sol-gel derived in situ fillers, metal salts of unsaturated carboxylic acids as well as the formation of interpenetrating networks with resins in detail.

For the design of stretchable and flexible high-performing materials, the reinforcement of elastomeric grades plays a crucial role. State-of-the-art fillers such as carbon black benefit from a high reinforcement but often negatively affect the processing and mixing properties of rubber compounds. To overcome this drawback, the synergistic properties of hybrid in situ filler systems are studied for EPDM compounds comprising a phenol novolac resin and ionic coagents such as zinc (meth)acrylates (ZD(M)A. With the help of a combined novolac/ZD(M)A system, the compounds could be tailored in a unique way towards higher toughness and enhanced cross-link density. Further, the fracture surface of the EPDM–novolac compounds was analyzed by scanning electron microscopy, revealing a significant change of the morphology from rough and disordered to smooth and homogenous for samples with coagents. In addition, the results clearly showed that the introduction of ionic coagents is able to compensate shares of carbon black filler in the EPDM compound. The toughening of samples with zinc (meth)acrylates is attributed to the synergistic formation of an interpenetrating polymer-filler network by simultaneous covalent and ionic cross-linking.

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