We have employed computational methods to investigate the iridium-catalyzed allylic substitution leading to the formation of enantioenriched allyl carbamates from carbon dioxide (CO₂). The reaction occurs in several steps, with initial formation of an iridium-allyl, followed by nucleophilic attack by the carbamate formed in situ from CO₂ and an amine. A detailed isomeric analysis ...

Silicon compounds containing silicon–silicon bond with a variety of unusual oxidation states are quite important, because their high reactivity leads to the formation of a variety of silicon compounds. The isolation of such compounds with unusual oxidation states requires a resilient synthetic strategy. Herein, we report the synthesis of a silicon based spirocyclic compound containing a hyper-valent ...

In the last decades, material discovery has been a very active research field driven by the need to find new materials for many different applications. This has also included materials with heavy elements, beyond the stable isotopes of lead, as most actinides exhibit unique properties that make them useful in various applications. Furthermore, new heavy elements beyond actinides, collectively referred ...

The current study evaluated a three-stage treatment to remediate PFAS-contaminated soil. The treatment consisted of soil washing, foam fractionation (FF), and electrochemical oxidation (EO). The possibility of replacing the third stage, i.e., EO, with an adsorption process was also assessed. The contamination in the studied soils was dominated by perfluorooctane sulfonate (PFOS), with a concentration ...

Phlorins have long remained underexplored relative to their fully conjugated counterparts, such as porphyrins, hydroporphyrins, and corroles. Herein, we have attempted to bridge that knowledge gap with a scalar-relativistic density functional theory (DFT) study of unsubstituted iridium and gold phlorin derivatives and a multitechnique experimental study of iridium-bispyridine and gold complexes of ...

This review covers the latest developments in the synthesis of cryptophane host molecules since the publication of the last extensive review by Brotin and Dutasta in 2009. The literature has been categorized according to the synthetic method for generating the cryptophane core and we also emphasize emerging late-stage functionalization approaches. The synthetic strategies towards cryptophanes ...

The boracarboxylation reaction has potential for the production of natural products and drug candidates, but the development of an asymmetric version of this transformation is challenging. We report an enantioselective boracarboxylation of styrenes, enabled by a copper catalyst containing chiral phosphines. Our experimental conditions provide yields between 31–76% and enantiomeric ratios from ...

A recent reinvestigation of the gas-phase photoelectron spectra of Group 6 metal−metal quadruple-bonded complexes with scalar-relativistic DFT calculations showed that common exchange-correlation functionals reproduce the lowest ionization potentials in a semiquantitative manner. The finding encouraged us to undertake a DFT study of metal− metal quintuple bonds in a set of bisamidinato complexes ...

We have revisited the gas-phase photoelectron spectra of quadruplebonded dimolybdenum(II,II) and ditungsten(II,II) paddlewheel complexes with modern density functional theory methods and obtained valuable calibration of four well-known exchange−correlation functionals, namely, BP86, OLYP, B3LYP*, and B3LYP. All four functionals were found to perform comparably, with discrepancies between calculated ...

Relativistic DFT (OLYP-D3/ZORA-STO-TZ2P) calculations predict low adiabatic ionization potentials for gold(II) porphyrins, from 4.60 eV for Au[TPP] (TPP = tetraphenylporphyrin) to 5.34 eV for Au[TPFPP] [TPFPP = tetrakis(pentafluorophenyl)porphyrin]. These values are over 1 eV lower than those calculated for analogous silver(II) porphyrins, reflecting much greater relativistic destabilization of ...