Acetylene Dithiolate Linking up the [Tp′W(CO)(CN)] Moiety with RuII or PdII

A series of heterodinuclear complexes with acetylene dithiolate (acdt^2?) as the bridging moiety were synthesised by a facile one‐pot procedure that avoided use of the highly elusive acetylene dithiol. Generation of the W–Ru complex [Tp′W(CN)(CO)(C₂S₂)Ru(η⁵‐C₅H₅)(PPh₃)] (Tp’=hydrotris(3,5‐dimethylpyrazolyl)borate) and the W–Pd complexes [Tp′W(CN)(CO)(C₂S₂)Pd(dppe)] and [Tp′W(CO)₂(C₂S₂)Pd(dppe)][PF₆] (dppe=1,2‐bis(diphenylphoshino)ethane), which exhibit a [W(η²‐κ²‐C₂S₂)M] core (M=Ru, Pd), was accomplished by using a transition‐metal‐assisted solvolytical removal of the Me₃Si‐ethyl thiol protecting groups. All intermediate species of the reaction have been fully characterised. The highly coloured W–Ru complex [Tp′W(CN)(CO)(C₂S₂)Ru(η⁵‐C₅H₅)(PPh₃)] shows reversible redox chemistry, as does the prototype complex [Tp′W(CO)₂(C₂S₂)Ru(η⁵‐C₅H₅)(PPh₃)][PF₆]. Single crystal X‐ray diffraction and IR, EPR and UV/Vis spectroscopic studies in conjunction with DFT calculations prove the high electronic delocalisation of states over the acdt^2? linker. Comparative studies revealed a higher donor strength and more pronounced dithiolate character of acdt^2? in [Tp′W(CN)(CO)(C₂S₂)Ru(η⁵‐C₅H₅)(PPh₃)] relative to [Tp′W(CO)₂(C₂S₂)Ru(η⁵‐C₅H₅)(PPh₃)]⁺. In addition, the influence of the overall complex charge on the metric parameters was investigated by single‐crystal X‐ray diffraction studies with the W–Pd complexes [Tp′WL₂(C₂S₂)Pd(dppe)] (L=(CN^?)(CO) or (CO)₂). The central [W(C₂S₂)Pd] units exhibit high structural similarity, which indicates the extensive delocalisation of charge over both metals.     

Decorrelation of networked communication flow via load-dependent routing weights

Clever assignments of link weights are able to change communication routes in such a way that loads are distributed almost evenly across a network. This is achieved by weight assignments based on the link load. As demonstrated for scale-free as well as synthetic Internet networks, they decorrelate the loads of the nodes and links from the network structure and increase the transport capacity of the network. For various Internet scans the increase of transport capacity amounts to a factor of around five when compared to shortest-path routing.     

ChemInform Abstract: An ab initio Investigation of Bismuth Hydration.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

Head-to-Tail Dimerization of N-Heterocyclic Diazoolefins

The head-to-tail dimerization of N-heterocyclic diazoolefins is described. The products of these formal (3+3) cycloaddition reactions are strongly reducing quinoidal tetrazines. Oxidation of the tetrazines occurs in a stepwise fashion, and we were able to isolate a stable radical cation and diamagnetic dications. The latter are also accessible by oxidative dimerization of diazoolefins.     

Bulk and surface properties of blends with semifluorinated polymers and block copolymers

The goal of the investigation presented here is the development of extremely hydrophobic materials based on polysulfone that can be applied, for instance, as fouling-resistant membrane materials. The concept used is the addition of semifluorinated polymers to polysulfone in suitable blend compositions. The influence of molecular parameters like chain structure of the semifluorinated polymer (segmented block copolymers, random copolymers) and segment molecular weight on the state of phase separation in the bulk and its influence on the surface properties have been systematically examined. It could be shown that segmented block copolymers with semifluorinated polyester segments with intermediate segment molecular weight are more suitable in blends with polysulfone than random polysulfone copolymers having semifluorinated side chains with respect to form homogeneous thin films (coatings) with highly non-wetting properties.