Disubstituted imidazolium-2-carboxylates as efficient precursors to N-heterocyclic carbene complexes of Rh, Ru, Ir, and Pd

N,N'-Disubstituted imidazolium-2-carboxylates are efficient precursors to NHC complexes of Rh, Ir, Pd, and Ru.     

An anion-dependent switch in selectivity results from a change of C-H activation mechanism in the reaction of an imidazolium salt with IrH5(PPh3)2

Changing the counteranion along the series Br, BF4, PF6, SbF6 in their ion-paired 2-pyridylmethyl imidazolium salts causes the kinetic reaction products with IrH5(PPh3)2 to switch from chelating N-heterocyclic carbenes (NHCs) having normal C2 (N path) to abnormal C5 binding (AN path). Computational work (DFT) suggests that the AN path involves C-H oxidative addition to Ir(III) to give Ir(V) with little anion dependence. The N path, in contrast, goes by heterolytic C-H activation with proton transfer to the adjacent hydride. The proton that is transferred is accompanied by the counteranion in an anion-coupled proton transfer, leading to an anion dependence of the N path, and therefore of the N/AN selectivity. The N path goes via Ir(III), not Ir(V), because the normal NHC is a much less strong donor ligand than the abnormal NHC. PGSE NMR experiments support the formation of ion-pair in both the reactants and the products. 19F,1H-HOESY NMR experiments indicate an ion-pair structure for the products that is consistent with the computational prediction (ONIOM(B3PW91/UFF)).     

Minimal mechanisms for school formation in self-propelled particles

In the context of social organisms, a school refers to a cohesive group of organisms that share a common speed and direction of motion, as well as a common axis of body alignment or polarization. Schools are also noted for the relatively fixed nearest-neighbour distances between individuals. The rules of interaction that lead to the formation and maintenance of a school structure have been explored experimentally, analytically, and by simulation. Interest in biological examples, and non-biological “self-propelled particles” such as robots, vehicles, or autonomous agents leads to the question of what are the simplest possible sets of rules that can assure the formation and the stability of the “perfect school”: an aggregate in which the nearest-neighbour distances and speeds are identical.Here we explore mechanisms that lead to a perfect school structure in one and two dimensions. We consider distance-detection as well as velocity-detection between the interacting pairs of self-propelled particles. We construct interaction forces and formulate schooling equations. In the simplest cases, these equations have analytic solutions. In many cases, the stability of the perfect school can be explored. We then investigate how these structures form and evolve over time from various initial configurations using simulations. We study the relationship between the assumed interaction forces and the school patterns that emerge. While true biological schools are far from perfect, the insights gained from this investigation can help to understand some properties of real schools, and to suggest the appropriate properties of artificial schools where coordinated motion is desired.     

Online variable-sized bin packing with conflicts

We study a new kind of online bin packing with conflicts, motivated by a problem arising when scheduling jobs on the Grid. In this bin packing problem, the set of items is given at the beginning, together with a set of conflicts on pairs of items. A conflict on a pair of items implies that they cannot be assigned to a common bin. The online scenario is realized as follows. Variable-sized bins arrive one by one, and items need to be assigned to each bin before the next bin arrives. We analyze the online problem as well as semi-online versions of it, which are the variant where the sizes of the arriving bins are monotonically non-increasing as well as the variant where they are monotonically non-decreasing.     

Mukaiyama-Michael vinylogous additions to nitroalkenes under solvent-free conditions

The first Mukaiyama-Michael vinylogous reaction of a dioxinone-derived silyl ether to nitroalkenes is reported. The conjugate addition is performed in absence of any catalyst under solvent-free conditions, proceeding with satisfactory efficiency with variously substituted nitroalkenes.     

On two-transitive ovals in projective planes of even order

In memoria di Paola Biscarini