Abstract Quantum mechanical tunneling (QMT) is the mechanism by which a particle can pass through a high potential energy barrier. Although rooted in quantum physics, QMT influences key chemical reactions in a number of ways. Here, we show that a new iridium dihydride complex IrH2 bearing a N,B-bid…
Abstract Four cis-chelating diphosphanes derived from cyclodextrins (CDs), each featuring a distinct intracavity environment, compel NiII or PdII metal centers to reside within α- or β-CD cavities. Nickel(II) complexes of these metal-confining ligands act as active catalysts in ethylene…
Abstract Oxidatively induced reductive elimination (OIRE) has become a crucial chemical process to enable the effective formation of otherwise much less accessible products. The chemically, electrochemically, or photochemically triggered oxidation of appropriate metal complexes leading to a…
Abstract Organofluorines have a broad range of industrial applications, such as pharmaceutics, liquid crystal displays (LCD), solar cells, textiles, and construction coatings, and are used in peptidomimetics, surfactants, refrigerants, anesthetics, and agrochemicals. Among them are versatile…
Abstract This study addresses the chemoselectivity of the catalyzed reduction of a series of variously substituted γ-lactams by Et3SiH mediated by a pentamethylcyclopentadienyl iridacyclic acetonitrilo salt derived from benzo[h]quinoline. Introduction of an unsaturation within the 5-membered ring…
Abstract Telluronium salts [Ar2MeTe]X were synthesized and their Lewis acidic properties towards a number of Lewis bases were addressed in solution by physical and theoretical means. The structural X-ray diffraction analysis of 21 different salts revealed the electrophilicity of the Te centers in…
Abstract The performance of six newly synthesized benzo[h]quinoline-derived acetonitrilo pentamethylcyclopentadienyl iridium(III) tetrakis(3,5-bis-trifluoromethylphenyl)borate salts bearing different substituents -X (-OMe, -H, -Cl, -Br, -NO2 and –(NO2)2) on the heterochelating ligand…
Abstract Miniaturized NMR (Nuclear Magnetic Resonance) devices are a trend in the industry because they allow a flexible use within a range of applications that would be otherwise not feasible with standard NMR equipment. However, one of the main obstacles in the development of miniaturized NMR…
Abstract Exploration of new organometallic systems based on polyhedral boron clusters has the potential to solve challenging chemical problems such as the stabilization of reactive intermediates and transition7 state-like species postulated for E−H (E = H, B, C, Si) bond activation reactions. We…
Abstract In this joint theoretical and experimental study, the analysis of weak interligand noncovalent interactions within Co(IV) [Cp*Co(phpy)X]+ cobaltacycles (phpy = 2-phenylenepyridine, κC,N) was carried out using the the Independent Gradient Model/Intrinsic Bond Strength Index (IGM/IBSI)…
Abstract The theory developed in an accompanying paper [Déjardin, Phys. Rev. E105, 024109 (2022)] is used to compute the Kirkwood correlation factor of simple polar fluids of different nature. From this calculation, the theoretical static permittivity is readily obtained, which is compared with…
Abstract In an effort to determine the thermochemistry of established organometallic transformation, the well documented reaction of alkynes with a palladacycle was investigated by isothermal titration calorimetry (ITC). Although the mechanism of the insertion of unsaturated substrates into the…
Abstract : Recent reports have identified Cp*Co-based complexes to be powerful catalysts for aromatic C–H bond activation under oxidative conditions. However, little is known about the speciation of Cp*Co species during catalysis. We now show that key intermediates, Cp*CoIII metallacycles derived…
Abstract The thermochemistry of the aminolysis of three methoxy Fischer carbenes, pentacarbonyl(phenylmethoxyalkylidene)chromium(0), tungsten(0) and molybdenum(0), was studied experimentally and theoretically with three amines, namely benzylamine, aniline and 3-pyrroline. Enthalpies of reactions…
Abstract The base-assisted cyclometalation of 2-phenylpyridine (2-phpyH) by Cp*Co(III) was holistically addressed both theoretically and experimentally. Combined DFT and DLPNO-CCSD(T) methods assisted by QTAIM-based noncovalent interactions plots (NCI plots), interacting quantum atoms (IQA), and…
Abstract To figure out the possible role of 1,1,1,3,3,3‐hexafluoropropan‐2‐ol (HFIP) as well as to provide reference thermochemical data in solution, the formation of Lewis acid‐base complexes between HFIP (Lewis acid) and a series of 8 different Lewis bases (3 sulfoxides, 3 Nsp2 pyridine…
Abstract The pentamethylcyclopentadienyl N‐heterocyclic carbene nickel complex [Ni(η 5 ‐C 5 Me 5 )Cl(IMes)] (IMes = 1,3‐dimesitylimidazol‐2‐ylidene) efficiently catalyses the anti‐Markovnikov hydroboration of alkenes with catecholborane in the presence of a catalytic amount of potassium tert…
Abstract The CMD/AMLA mechanisms of cyclopalladation and the parent fictitious but challenging cyclonickelation of N,N-dimethylbenzylamine have been investigated by joint DFT-D and DLPNO-CCSD(T) methods assisted by QTAIM-based noncovalent interaction plots (NCI plots) and interacting quantum atoms…
Abstract Two new trimetallic Cr‐Pd hemichelates containing a fluorenyl moiety and two trans arene‐bound Cr(CO)3 moieties were synthesized and fully characterized. Their molecular structures obtained by X‐ray diffraction analysis do not show major differences – in interatomic bond lengths within…
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