Bis‐NHC Chelate Complexes of Nickel(0) and Platinum(0)

For a long time d¹⁰‐ML₂ fragments have been known for their potential to activate unreactive bonds by oxidative addition. In the development of more active species, two approaches have proven successful: the use of strong σ‐donating ligands leading to electron‐rich metal centers and the employment of chelating ligands resulting in a bent coordination geometry. Combining these two strategies, we synthesized bis‐NHC chelate complexes of nickel(0) and platinum(0). Bis(1,5‐cyclooctadiene)nickel(0) and ‐platinum(0) react with bisimidazolium salts, deprotonated in situ at room temperature, to yield tetrahedral or trigonal‐planar bis‐NHC chelate olefin complexes. The synthesis and characterization of these complexes as well as a first example of C? C bond activation with these systems are reported. Due to the enforced cis arrangement of two NHCs, these compounds should open interesting perspectives for bond‐activation chemistry and catalysis.     

Reactivity of Binary and Ternary Sulfur Halides towards Transition-Metal Compounds

Binary sulfur fluorides exhibit an interesting reactivity towards transition metal complexes. They open up routes for the generation of sulfur-containing building blocks. Often ligands with particular properties can be constructed. This includes their ability to transfer sulfur atoms or polysulfide units as well as fluorination reactions. This Minireview provides an insight into the reactivity of the binary and ternary sulfur halides S₂Cl₂, SCl₂, SF₄, SF₆ and SF₅Cl towards transition-metal compounds.     

Measures of periodicity for time series analysis of threshold-crossing events

Large-amplitude climate shifts, the so-called Dansgaard-Oeschger events, repeatedly occurred throughout the last ice age. These events, which are apparently threshold-crossing events, show a reported tendency to recur preferably in near multiples of about 1470 years. Several non-linear resonance mechanisms were proposed to explain this recurrence pattern in response to noise and/or periodic forcing. Standard methods of linear time series analysis are not sufficient to distinguish between these hypotheses, owing to the threshold-crossing dynamics of the events. Recently, new approaches were made by means of null-hypothesis testing with Monte Carlo methods. A major hurdle in this approach is the need of efficient, but yet simple measures of regularity that allow to distinguish between the proposed resonance mechanisms. By means of surrogate time series (i.e. by using a large ensemble of Dansgaard-Oeschger events as simulated with a very simple two-state model) I here test the ability of three standard measures of periodicity to distinguish between a scenario of solely noise-induced events and a ghost stochastic resonance scenario. Only one measure is found to be applicable for that purpose. The choice of adequate measures, which is not trivial, should be given more attention in future studies that focus on the question what triggered threshold-crossing events such as Dansgaard-Oeschger events.     

Odderon with a running coupling constant

The running coupling is introduced into the equation for the odderon via the bootstrap relation. It is shown that the previously found odderon state with a maximal intercept, which is constructed from an antisymmetric pomeron wave function, continues to exist in the running coupling case. Its intercept is found to remain equal to unity independent of the behaviour assumed for the running coupling at low momenta.     

The first coordination compound containing three different types of spin carriers: 2p-3d-4f (TCNQ.-, Cu2+ and Gd3+)

A novel heterospin system, [(CuL)2Gd(TCNQ)2].TCNQ-.CH3OH.2CH3CN, is obtained by reacting the mononuclear complex, [CuL], with gadolinium(III) nitrate, followed by the substitution of the nitrato ions with anionic organic radicals.     

Atomic-scale structure of dislocations revealed by scanning tunneling microscopy and molecular dynamics

The intersection between dislocations and a Ag(111) surface has been studied using an interplay of scanning tunneling microscopy (STM) and molecular dynamics. Whereas the STM provides atomically resolved information about the surface structure and Burgers vectors of the dislocations, the simulations can be used to determine dislocation structure and orientation in the near-surface region. In a similar way, the subsurface structure of other extended defects can be studied. The simulations show dislocations to reorient the partials in the surface region leading to an increased splitting width at the surface, in agreement with the STM observations. Implications for surface-induced cross slip are discussed.     

New oxidative transformations of phenolic and indolic oxazolines: an avenue to useful azaspirocyclic building blocks

The oxidative cyclization of a phenolic amide to a spirolactam has long been regarded as an "impossible" reaction, because exposure of the substrates to a variety of oxidants results in formation of spirolactones with consequent loss of the amine segment. We recently communicated that this heretofore unknown transformation may be achieved by oxidation of oxazoline analogues of phenolic and indolic amides. Herein, we provide full details of our work.     

Nickel-Assisted Carbon-Fluorine Bond Activation of 2,4,6-Trifluoropyrimidine: Synthesis of New Pyrimidine and Pyrimidinone Derivatives

Rapid and regioselective activation of the C-F bond of 2,4,6-trifluoropyrimidine occurs on reaction with [Ni(cod)(2)] (cod=1,5-cyclooctadiene) in the presence of PEt(3) to give 1, which can be converted into complex 2, containing a further N(3)-metalated pyrimidin-4-one unit. The novel pyrimidin-4-one 3 is released on protonation of 2.