A5089252286- X-ray Diffraction in Crystallography
- Crystallization and Solubility Studies
- Silicon Carbide Semiconductor Technologies
- Organometallic Complex Synthesis and Catalysis
- Semiconductor materials and devices
- Asymmetric Hydrogenation and Catalysis
- Spectroscopy and Quantum Chemical Studies
- Crystallography and molecular interactions
- Advanced Chemical Physics Studies
- Synthesis and characterization of novel inorganic/organometallic compounds
- Organoboron and organosilicon chemistry
- Advanced NMR Techniques and Applications
- Porphyrin and Phthalocyanine Chemistry
- Advancements in Semiconductor Devices and Circuit Design
- Semiconductor materials and interfaces
- Metal-Catalyzed Oxygenation Mechanisms
- Carbon Nanotubes in Composites
- Electromagnetic Compatibility and Noise Suppression
- Coordination Chemistry and Organometallics
- Synthetic Organic Chemistry Methods
- N-Heterocyclic Carbenes in Organic and Inorganic Chemistry
- Chemical and Physical Properties in Aqueous Solutions
- Chemical Synthesis and Analysis
- Inorganic Fluorides and Related Compounds
- Copper Interconnects and Reliability
Institut Charles Gerhardt Montpellier
2008-2025
Réseau sur le Stockage Electrochimique de l'énergie
2025
Université de Montpellier
2015-2024
Centre National de la Recherche Scientifique
2015-2024
École Nationale Supérieure de Chimie de Montpellier
2008-2024
Laboratoire Ampère
2004-2020
Université Paris Cité
2014-2020
Délégation Paris 7
2019-2020
École Normale Supérieure
2019
Institut National des Sciences Appliquées de Lyon
1994-2018
The nucleophilic carbon of d0 Schrock alkylidene metathesis catalysts, [M] = CHR, display surprisingly low downfield chemical shift (δiso) and large anisotropy. State-of-the-art four-component relativistic calculations the tensors combined with a two-component analysis in terms localized orbitals allow molecular-level understanding their orientations, magnitude principal components (δ11 > δ22 δ33) associated δiso. This reveals dominating influence paramagnetic contribution yielding highly...
ConspectusMetal-bonded carbon atoms in metal–alkyl, metal–carbene/alkylidene, and metal–carbyne/alkylidyne species often show significantly more deshielded isotropic chemical shifts than their organic counterparts (alkanes, alkenes, alkynes). While shift is universally used to characterize a compound solution, it an average value of the three principal components tensor (δ11 > δ22 δ33). The components, which are accessible by solid-state NMR spectroscopy, can provide detailed information...
The narrow emission of a single carbon nanotube at low temperature is coupled to the optical mode fiber microcavity using built-in spatial and spectral matching brought by this flexible geometry. A thorough cw time-resolved investigation very same emitter both in free space cavity shows an efficient funneling into together with strong enhancement corresponding Purcell factor up 5. At time, emitted photons retain sub-Poissonian statistics. By exploiting feeding effect on phonon wings, we...
Metallacyclobutanes are an important class of organometallic intermediates, due to their role in olefin metathesis. They can have either planar or puckered rings associated with characteristic chemical and physical properties. Metathesis active metallacyclobutanes short M-Cα/α' M···Cβ distances, long Cα/α'-Cβ bond length, isotropic 13C shifts for both early d0 late d4 transition metal compounds the α- β-carbons appearing at ca. 100 0 ppm, respectively. that do not show metathesis activity...
Molybdenum-based molecular alkylidyne complexes of the type [MesC≡Mo{OC(CH3)3–x(CF3)x}3] (MoF0, x = 0; MoF3, 1; MoF6, 2; MoF9, 3; Mes 2,4,6-trimethylphenyl) and their silica-supported analogues are prepared characterized at level, in particular by solid-state NMR, alkyne metathesis catalytic activity is evaluated. The 13C NMR chemical shift carbon increases with increasing number fluorine atoms on alkoxide ligands for both supported catalysts but more shielded values complexes. these order...
We describe competitive C−H bond activation chemistry of two types, desaturation and hydroxylation, using synthetic manganese catalysts with several substrates. 9,10-Dihydrophenanthrene (DHP) gives the highest activity, final products being phenanthrene (P1) 9,10-oxide (P3), latter thought to arise from epoxidation some phenanthrene. The hydroxylase pathway also occurs as suggested by presence dione product, phenanthrene-9,10-dione (P2), further oxidation hydroxylation intermediate...
Abstract Fischer and Schrock carbenes display highly deshielded carbon chemical shifts (>250 ppm), in particular (>300 ppm). Orbital analysis of the principal components shift tensors determined by solid‐state NMR spectroscopy calculated a 2‐component DFT method shows specific patterns that act as fingerprints for each type complex. The calculations highlight role paramagnetic term shielding tensor especially two most (σ 11 σ 22 ). is dominated coupling σ(M=C) with π*(M=C) through...
Oxyl radical character in the MnO group of title system is shown from a density functional theory study to be essential for efficient C-H cleavage, which key step oxidation. Since oxyl species have elongated Mn-O bonds relative more usual oxo type MnO, normal expectation would that high trans-influence ligands X should facilitate by elongating bond and thus enhance both reactivity. Contrary this expectation, but line with experimental data (Jin, N.; Ibrahim, M.; Spiro, T. G.; Groves, J. Am....
We present, for the first time, scalable polarizable molecular dynamics (MD) simulations within a continuum solvent with shape cavities and exact solution of mutual polarization. The key ingredients are very efficient algorithm solving equations associated continuum, in particular, domain decomposition Conductor-like Screening Model (ddCOSMO), which involves rigorous coupling force field achieved through robust variational formulation an effective strategy to solve coupled equations. ddCOSMO...
DFT studies show that the rebound mechanism for MnO(tpp)(Cl)-catalyzed C-H hydroxylation is favored spin states with oxyl character.
Abstract Tuning the nature of linker in a L∼BHR phosphinoborane compound led to isolation ruthenium complex stabilized by two adjacent, δ‐CH and ε‐B sp2 H, agostic interactions. Such unique coordination mode stabilizes 14‐electron “RuH 2 P ” fragment through connected σ‐bonds different polarity, affords selective BH, CH, BC bond activation as illustrated reactivity studies with H boranes.
An intramolecular 1,2(α)-H migration in a saturated ruthenium stannylene complex, to form ruthenostannylene involves reversal of the role for coordinated ligand, from that an electron donor acceptor transition state. This change bonding properties group, with simple molecular motion, lifts usual requirement generation unsaturated metal center chemistry.
The accurate modeling of solvent dynamics and ionic interactions is crucial importance for the development novel electrolytes in next-generation metal-ion batteries. This study presents a critical evaluation semi-classical computational approach, adaptive Quantum Thermal Bath (adQTB) method, as methodology capturing key properties glyme-based solvents their Ca2+-based electrolyte solutions. Simulations reveal that adQTB method particularly effective accurately reproducing vibrational...
The accurate modeling of solvent dynamics and ionic interactions is crucial importance for the development novel electrolytes in next-generation metal-ion batteries. This study presents a critical evaluation semi-classical computational approach, adaptive Quantum Thermal Bath (adQTB) method, as methodology capturing key properties glyme-based solvents their Ca2+-based electrolyte solutions. Simulations reveal that adQTB method particularly effective accurately reproducing vibrational...
A DFT study on toluene oxidation by Mn(V) porphyrins shows that both MnV(O) and, remarkably, MnV(OH) are potent H-atom abstractors.
A reconsideration of Car–Parrinello molecular dynamics using only atom centred basis functions is presented by doing direct propagation orbitals in conjunction with nuclei. The electronic degree freedom chosen for the are coefficients linear combination atomic development where expressed upon Gaussian functions. Considering that wave function propagated, we show very few iterations sufficient to calculate nuclear gradients and potential energy good accuracy, instead fulfilling minimisation...
The synthesis of the cyclometalated complexes Cp*Ru(IXy-H) (2) [IXy = 1,3-bis(2,6-dimethylphenyl)imidazol-2-ylidene; IXy-H 1-(2-CH2C6H3-6-methyl)-3-(2,6-dimethylphenyl)imidazol-2-ylidene-1-yl (the deprotonated form IXy); Cp* η(5)-C5Me5] and Cp*Ru(IXy-H)(N2) (3) was achieved by dehydrochlorination Cp*Ru(IXy)Cl (1) with KCH2Ph. Complexes 2 3 activate primary silanes (RSiH3) to afford silyl Cp*(IXy-H)(H)RuSiH2R [R p-Tol (4), Mes (5), Trip (6)]. Density functional theory studies indicated that...
The halogen bond (XB) is a highly directional class of noncovalent interactions widely explored by experimental and computational studies. However, the NMR signature XB has attracted limited attention. prediction analysis solid-state (SSNMR) chemical shift tensor provide useful strategies to better understand interactions. In this work, we employ protocol for modeling analyzing 19F SSNMR shifts previously measured in family square-planar trans NiII-L2-iodoaryl-fluoride (L = PEt3) complexes...
Experimental studies have shown that the C–H oxidation of Ibuprofen and methylcyclohexane acetic acid can be carried out with high selectivities using [(terpy')Mn(OH2)(μ-O)2Mn(OH2)(terpy')]3+ as catalyst, where terpy' is a terpyridine ligand functionalized phenylene linker Kemp's triacid serving to recognize reactant viaH-bonding. Experiments, described here, suggest sulfate counter anion, present in stochiometric amounts, coordinates manganese place water. DFT calculations been...
Relativistic DFT calculations rationalise hydride NMR chemical shifts in a range of Ru complexes.
Classical molecular dynamics (MD) simulations of electrolyte systems are important to gain insight into the atom-scale properties that determine battery-relevant performance. The recent Tinker-HP software release enables efficient and accurate MD with AMOEBA polarizable force field. In this work, we developed a procedure construct universal model for solvent family glymes (glycol methyl ethers), which involves refinement scheme valence parameters by fitting AMOEBA-derived atomic forces those...
Abstract Fischer and Schrock carbenes display highly deshielded carbon chemical shifts (>250 ppm), in particular (>300 ppm). Orbital analysis of the principal components shift tensors determined by solid‐state NMR spectroscopy calculated a 2‐component DFT method shows specific patterns that act as fingerprints for each type complex. The calculations highlight role paramagnetic term shielding tensor especially two most (σ 11 σ 22 ). is dominated coupling σ(M=C) with π*(M=C) through...