Lewis acids (LAs) have been shown to accelerate hydrogenation of C0₂, but the underlying mechanistic details remain to be elucidated. We have employed computational methods to investigate how LAs affect CO₂ hydrogenation with a range of known metal-hydrides (L_nIr–H, L_nRu–H, L_nMn–H, L_nCo–H). Our results show that LAs can alter the ...

A combination of quantum chemical calculations and synthetic studies was used to address the possibility of very high (>6) valence states of transition metals in porphyrin‐type complexes. With corrole as a supporting ligand, DFT calculations ruled out Re(VII) and Ir(VII) dioxo complexes as stable species. Attempted rhenium insertion into benzocarbaporphyrin (BCP) ligands on the other hand led to two ...

The criteria for defining bacterial species and even the concept of bacterial species itself are under debate, and the discussion is apparently intensifying as more genome sequence data is becoming available. However, it is still unclear how the new advances in genomics should be used most efficiently to address this question. In this study we identify genes that are common to any group of genomes ...

Zero-point vibrational (ZPV) corrections to the nuclear spin–spin coupling constants have been calculated using four-component Dirac–Kohn–Sham DFT for H₂X (where X = O, S, Se, Te, Po), XH₃ (where X = N, P, As, Sb, Bi), and XH₄ (where X = C, Si, Ge, Sn, and Pb) molecules and for HC≡CPbH₃. The main goal was to study the influence of relativistic effects on ...

Sulfoxonium ylides have recently gained prominence as safe carbenoid precursors in metal-catalyzed reactions. The stability and reactivity of sulfoxonium ylides depend on the substitution of the ylide carbon. The reactivity of vinyl-substituted sulfoxonium ylides is different and offers several advantages over known stabilized sulfoxonium ylides in the case of carbenoid transfer reactions. Herein, ...

Herein is disclosed a novel visible-light photocatalytic double C–H functionalization of indoles. The reaction affords 2,3-difunctional- ized indoles in up to 84% yield, but the reaction rate depends strongly on electronic substituent effects. Mechanistic DFT studies and control experiments suggest that the secondary functionalization occurs through an independent photocatalytic oxidation ...

The solution of the Liouville–von Neumann equation in the relativistic Dirac–Kohn–Sham density matrix formalism is presented and used to calculate X-ray absorption cross sections. Both dynamical relaxation effects and spin–orbit corrections are included, as demonstrated by calculations of the X-ray absorption of SF6 near the sulfur L2,3-edges. We also propose an analysis facilitating the interpretation ...

A combination of Cr K-edge XAS and DFT calculations have been performed on archetypal chromium porphyrinoid complexes Cr^IV[TMP]O (<b>2</b>) and Cr^V[TPC]O (<b>3</b>), and the results have been compared to the reference compound Cr^III[TPP]Cl (<b>1</b>), where TPP²⁻, TMP²⁻, and TPC³⁻ are the anions of <i>meso</i>-tetraphenylporphyrin, ...

<i>Background</i> - <i>Para</i>-nitrophenyl phosphate, the common substrate for alkaline phosphatase (AP), is available as a cyclohexylamine salt. Here, we report that cyclohexylamine is a non-competitive inhibitor of APs.<br><br> <i>Methods</i> - Cyclohexylamine inhibited four different APs. Co-crystallization with the cold-active <i>Vibrio</i> AP (VAP) was performed and the structure solved.<br><br> ...