UV stabilizers bonded to transition metals: Synthesis and X-ray structure of 2-(2′-hydroxyphenyl)benzotriazole-oxovanadium(IV) and -dioxomolybdenum(VI) complexes

The UV-stabilizer 2-(2′-hydroxy-5′-methylphenyl)benzotriazole (Tinuvin P, LH) has been used as a monoanionic bidentate ligand for complexing oxocations. Displacement of acacH from [VO(acac)₂] and [MoO₂(acac)₂] gave [*VO(acac)₂*(μ-L)] (2) and [cis-O₂Mo(acac)L] (3) respectively, as crystalline compounds. Their structure has been determined by an X-ray analysis showing the structural changes occurring upon coordination. The UV spectrum of Tinuvin P is significantly affected by complexation.     

Electrochemical behaviour of some polyoxo clusters

We describe the redox behaviour in non-aqueous solvents of some cyclopentadienyl(oxo)titanium derivatives. The derivative [Ti₄{η⁵-C₅H₄(SiMe₃)}₄(μ-O)₆] shows an electrochemically and chemically reversible le reduction process, followed by a multi-electron, chemically complicated reduction at a fairly cathodic potential. On the basis of the overall electrochemical features and the comparison with the redox behaviour of the quasi-planar compound [[Ti{η⁵-C₅H₄(SiMe₃)}Cl(μ-O)]₄] we propose an EECCEE mechanism for the first derivative, where the second electron-transfer induces a cascade of chemical reactions giving rise to irreversible cluster breakdown. The electrochemically induced fragmentation can be viewed as a retrosynthetic pathway. The heterometallic derivative [{Ti(η⁵-C₅H₄Me)₂(μ₂-MoO₄)₂}₂] shows two consecutive reduction processes; the first is chemically reversible, and the second quasi-reversible. The molybdate bridges apparently increase the stability of the electrogenerated anions. However none of these poly-oxo clusters can be considered as good models of electron ‘sinks’.     

Vector unparticle enhanced black holes: Exact solutions and thermodynamics

Tensor and scalar unparticle couplings to matter have been shown to enhance gravitational interactions and provide corrections to the Schwarzschild metric and associated black hole structure. We derive an exact solution to the Einstein equations for vector unparticles, and conclusively demonstrate that these induce Riessner–Nordström (RN)-like solutions where the role of the “charge” is defined by a composite of unparticle phase space parameters. These black holes admit double-horizon structure, although unlike the RN metric these solutions have a minimum inner horizon value. In the extremal limit, the Hawking temperature is shown to vanish. As with the scalar/tensor case, the (outer) horizon is shown via entropy considerations to behave like a fractal surface of spectral dimension dH=2dU$d_H=2d_U$.     

A self-assembled receptor for the recognition of phosphate and acetate anions in neutral aqueous solution

The reaction of [(benzene)RuCl(2)](2) with a piperazine-bridged bis(dihydroxypyridine) ligand and LiOH leads to the formation of an expanded helicate, which is able to bind phosphate and acetate in aqueous solution at neutral pH.     

Neutral,Cationic, and Anionic Alkyl Derivatives of Tungsten Bonded to a Calix[4]arene Oxo Surface

The chemically reversible reduction of [(Me)₂W(calix)] to the diamagnetic [(Me)₂W(calix)Na₂] [Eq. (1)], without major changes in the connectivity of the molecule, illustrates the flexibility of the calixarene ligand and stresses its potential as a molecular functional model of heterogeneous oxo surfaces.     

Functionalizable Alkylidenes: Tungsten Complexes of Phosphanyl-, Amino-, Alkynyl-, and Tinalkylidenes and Their Dimetallic Derivatization

The introduction of a heteroatom at the alkylidene carbon atom of calixarene complexes such as 1 results in an organometallic compound that shows properties of both Fischer carbenes and Schrock alkylidenes. Such modified alkylidenes allow access to dimetallic alkylidene complexes. For example, 1 reacts with [CuCOCl] to provide 2 .