Toward asymmetric aziridination with an iron complex supported by a -symmetric tetra-NHC.

A neutral -symmetric macrocyclic tetra-N-heterocyclic carbene ligand was synthesized. The macrocycle was ligated to iron(II) transmetalation from an isolated silver complex that has two conformers. The iron complex catalyzed the first stereospecific aziridination between aryl azides and aliphatic alkenes, albeit with low ee's.

Correction: Interfacial acidity on the strontium titanate surface: a scaling paradigm and the role of the hydrogen bond.

Correction for 'Interfacial acidity on the strontium titanate surface: a scaling paradigm and the role of the hydrogen bond' by Robert C. Chapleski, Jr. , , 2021, , 23478-23485, DOI: 10.

Interfacial acidity on the strontium titanate surface: a scaling paradigm and the role of the hydrogen bond.

A fundamental understanding of acidity at an interface, as mediated by structure and molecule-surface interactions, is essential to elucidate the mechanisms of a range of chemical transformations. While the strength of an acid in homogeneous gas and solution phases is conceptually well understood, acid-base chemistry at heterogeneous interfaces is notoriously more complicated. Using density functional theory and nonlinear vibrational spectroscopy, we present a method to determine the interfacial Brønsted-Lowry acidity of aliphatic alcohols adsorbed on the (100) surface of the model perovskite, strontium titanate.

Elucidation of the Reaction Mechanism of C + N Aziridination from Tetracarbene Iron Catalysts.

A combined computational and experimental study was undertaken to elucidate the mechanism of catalytic C + N aziridination supported by tetracarbene iron complexes. Three specific aspects of the catalytic cycle were addressed. First, how do organic azides react with different iron catalysts and why are alkyl azides ineffective for some catalysts? Computation of the catalytic pathway using density functional theory (DFT) revealed that an alkyl azide needs to overcome a higher activation barrier than an aryl azide to form an iron imide, and the activation barrier with the first-generation catalyst is higher than the activation barrier with the second-generation variant.

Catalytic aziridination with alcoholic substrates via a chromium tetracarbene catalyst.

The first examples of aziridination catalysis with a chromium complex are communicated. This tetracarbene chromium complex provides novel catalytic aziridination reactions with protic substrates such as alcohols or amines on the alkene or organic azide and is the most effective catalyst at low alkene loading for aliphatic alkenes to date.

Chemistry at molecular junctions: Rotation and dissociation of O2 on the Ag(110) surface induced by a scanning tunneling microscope.

The scanning tunneling microscope (STM) is a fascinating tool used to perform chemical processes at the single-molecule level, including bond formation, bond breaking, and even chemical reactions. Hahn and Ho [J. Chem.

Dynamical steering and electronic excitation in NO scattering from a gold surface.

Nonadiabatic coupling of nuclear motion to electronic excitations at metal surfaces is believed to influence a host of important chemical processes and has generated a great deal of experimental and theoretical interest. We applied a recently developed theoretical framework to examine the nature and importance of nonadiabatic behavior in a system that has been extensively studied experimentally: the scattering of vibrationally excited nitric oxide molecules from a Au(111) surface. We conclude that the nonadiabatic transition rate depends strongly on both the N-O internuclear separation and the molecular orientation and, furthermore, that molecule-surface forces can steer the molecule into strong-coupling configurations.

Model Hamiltonian for the interaction of NO with the Au(111) surface.

We have constructed a model Hamiltonian to describe the interaction of a nitric oxide (NO) molecule with a Au(111) surface. The diagonal elements of the 2x2 Hamiltonian matrix represent the diabatic potential energy surfaces corresponding to the neutral and negative-ion states of the molecule. A position-dependent off-diagonal element controls the extent of mixing of the two diabatic states.

Nonadiabatic dynamics at metal surfaces: independent-electron surface hopping.

Recent experiments have shown convincing evidence for nonadiabatic energy transfer from adsorbate degrees of freedom to surface electrons during the interaction of molecules with metal surfaces. In this paper, we propose an independent-electron surface hopping algorithm for the simulation of nonadiabatic gas-surface dynamics. The transfer of energy to electron-hole pair excitations of the metal is successfully captured by hops between electronic adiabats.

Vibrational relaxation of NO on Au(111) via electron-hole pair generation.

Recent experiments have demonstrated the breakdown of the Born-Oppenheimer approximation when NO undergoes inelastic scattering from a Au(111) surface. In this paper, we provide a simple theoretical model for understanding this phenomenon. Our model predicts multiquanta vibrational relaxation through the creation of high-energy electron-hole pair excitations in the metal.