Anomalous Negative Magnetoresistance Caused by Non-Markovian Effects

A theory of recently discovered anomalous low-field magnetoresistance is developed for the system of two-dimensional electrons scattered by hard disks of radius $a,$ randomly distributed with concentration $n.$ For small magnetic fields the magentoresistance is found to be parabolic and inversely proportional to the gas parameter, $\delta \rho_{xx}/\rho \sim - (\omega_c \tau)^2 / n a^2.$ With increasing field the magnetoresistance becomes linear $\delta \rho_{xx}/\rho \sim - \omega_c \tau$ in a good agreement with the experiment and numerical simulations.Comment: 4 pages RevTeX, 5 figure

Quasiclassical magnetotransport in a random array of antidots

We study theoretically the magnetoresistance $\rho_{xx}(B)$ of a two-dimensional electron gas scattered by a random ensemble of impenetrable discs in the presence of a long-range correlated random potential. We believe that this model describes a high-mobility semiconductor heterostructure with a random array of antidots. We show that the interplay of scattering by the two types of disorder generates new behavior of $\rho_{xx}(B)$ which is absent for only one kind of disorder. We demonstrate that even a weak long-range disorder becomes important with increasing $B$. In particular, although $\rho_{xx}(B)$ vanishes in the limit of large $B$ when only one type of disorder is present, we show that it keeps growing with increasing $B$ in the antidot array in the presence of smooth disorder. The reversal of the behavior of $\rho_{xx}(B)$ is due to a mutual destruction of the quasiclassical localization induced by a strong magnetic field: specifically, the adiabatic localization in the long-range Gaussian disorder is washed out by the scattering on hard discs, whereas the adiabatic drift and related percolation of cyclotron orbits destroys the localization in the dilute system of hard discs. For intermediate magnetic fields in a dilute antidot array, we show the existence of a strong negative magnetoresistance, which leads to a nonmonotonic dependence of $\rho_{xx}(B)$.Comment: 21 pages, 13 figure

Cobalt(II)–tetraphenylporphyrin-catalysed carbene transfer from acceptor–acceptor iodonium ylides via N-enolate–carbene radicals

Square-planar cobalt(II) systems have emerged as powerful carbene transfer catalysts for the synthesis of numerous (hetero)cyclic compounds via cobalt(III)–carbene radical intermediates. Spectroscopic detection and characterization of reactive carbene radical intermediates is limited to a few scattered experiments, centered around monosubstituted carbenes. Here, we reveal the formation of disubstituted cobalt(III)–carbene radicals derived from a cobalt(II)–tetraphenylporphyrin complex and acceptor–acceptor λ3-iodaneylidenes (iodonium ylides) as carbene precursors and their catalytic application. Iodonium ylides generate biscarbenoid species via reversible ligand modification of the paramagnetic cobalt(II)–tetraphenylporphyrin complex catalyst. Two interconnected catalytic cycles are involved in the overall mechanism, with a monocarbene radical and an N-enolate–carbene radical intermediate at the heart of each respective cycle. Notably, N-enolate formation is not a deactivation pathway but a reversible process, enabling transfer of two carbene moieties from a single N-enolate–carbene radical intermediate. The findings are supported by extensive experimental and computational studies. [Figure not available: see fulltext.

Cobalt(II)–tetraphenylporphyrin-catalysed carbene transfer from acceptor–acceptor iodonium ylides via N-enolate–carbene radicals

Square-planar cobalt(II) systems have emerged as powerful carbene transfer catalysts for the synthesis of numerous (hetero)cyclic compounds via cobalt(III)–carbene radical intermediates. Spectroscopic detection and characterization of reactive carbene radical intermediates is limited to a few scattered experiments, centered around monosubstituted carbenes. Here, we reveal the formation of disubstituted cobalt(III)–carbene radicals derived from a cobalt(II)–tetraphenylporphyrin complex and acceptor–acceptor λ3-iodaneylidenes (iodonium ylides) as carbene precursors and their catalytic application. Iodonium ylides generate biscarbenoid species via reversible ligand modification of the paramagnetic cobalt(II)–tetraphenylporphyrin complex catalyst. Two interconnected catalytic cycles are involved in the overall mechanism, with a monocarbene radical and an N-enolate–carbene radical intermediate at the heart of each respective cycle. Notably, N-enolate formation is not a deactivation pathway but a reversible process, enabling transfer of two carbene moieties from a single N-enolate–carbene radical intermediate. The findings are supported by extensive experimental and computational studies. [Figure not available: see fulltext.