Aurora_pyh

Nature Communications, Published online: 22 November 2019; doi:10.1038/s41467-019-13242-x

Sensing DNA bases by surface-enhanced Raman spectroscopy (SERS) in plasmonic nanopores has suffered from rapid flow through of molecules. Here, the authors attach DNA molecules to gold nanoparticles which, due to electro-plasmonic trapping, allow for controlled residence times and discrimination of single nucleotides.

The elusive HAs=AsH, the heavy analogue of ethylene, is side‐on coordinated by a 3d transition metal complex without using kinetic stabilisation. By methanolysis of [{Fe(CO)₄}As(SiMe₃)₃], the complex [{Fe(CO)₄}{η²‐As₂H₂}] was synthesized. DFT calculations show that the bonding mode can be best described by the Dewar–Chatt–Duncanson model. Subsequent reactivity studies reveal that it reacts as an AsH transfer reagent.

Abstract

The terminal diarsene HAs=AsH ligand attracts special interest concerning its bonding relation in comparison to its isolable relative, ethene. Herein, by the methanolysis of [{Fe(CO)₄}As(SiMe₃)₃] (1) the synthesis of [{Fe(CO)₄}(η²‐As₂H₂)] (2) is reported, containing a parent diarsene as unprecedented side‐on coordinated ligand. Following this synthetic route, also the D‐labeled complex [{Fe(CO)₄}(η²‐As₂D₂)] (2D) could be isolated. The electronic structure and bonding situation of 2 was elucidated by DFT calculations revealing that 2 is best described as an olefin‐like complex. Moreover, the reactivity of 2 towards the Lewis acids [{M(CO)₅}(thf)] (M=Cr, W) was investigated, leading to the complexes [Fe(CO)₄AsHW(CO)₅]₂ (3) and [{Fe(CO)₄}₂AsH{Cr(CO)₅}] (4), respectively.

Metal‐complex/semiconductor hybrid materials have attracted attention as new photocatalysts and photoelectrodes for visible‐light CO₂ reduction to carbon feedstocks, because they can utilize both the outstanding electrochemical (and/or photocatalytic) activity of metal complexes for CO₂ reduction and the strong photo‐oxidation ability of semiconductors. A critical overview of the development of hybrid photocatalysts and photoelectrodes for visible‐light CO₂ reduction is presented.

Abstract

CO₂ reduction to carbon feedstocks using heterogeneous photocatalysts is an attractive means of addressing both climate change and the depletion of fossil fuels. Of particular importance is the development of a photosystem capable of functioning in response to visible light, which accounts for the majority of the solar spectrum, representing a kind of artificial photosynthesis. Hybrid systems comprising a metal complex and a semiconductor are promising because of the excellent electrochemical (and/or photocatalytic) activity of metal complexes during CO₂ reduction and the ability of semiconductors to efficiently oxidize water to molecular O₂. Here, the development of hybrid photocatalysts and photoelectrodes for CO₂ reduction in combination with water oxidation is described.

When the fearless Don Quixote was charging at windmills, he left his slow companion, Sancho Panza, behind. In their Communication on https://doi.org/10.1002/anie.201812937page 1980 ff., X. Zhang, J. Sun et al. describe a novel rhodium‐catalyzed dearomatization and rearrangement of O‐substituted pyridines to access N‐substituted 2‐pyridones, a challenging target because their straightforward synthesis by simple alkylation of 2‐pyridones is thwarted by their preferred O‐reactivity. The key to this transformation is the formation of the pyridinium ylide and a subsequent 1,4‐acyl migratory rearrangement.

Abstract