A5077278493- Crystallography and molecular interactions
- Advanced Chemical Physics Studies
- Inorganic Fluorides and Related Compounds
- Molecular Junctions and Nanostructures
- Catalysis and Oxidation Reactions
- Synthesis and characterization of novel inorganic/organometallic compounds
- Molecular Sensors and Ion Detection
- Metal-Catalyzed Oxygenation Mechanisms
- Magnetism in coordination complexes
- Fuel Cells and Related Materials
- Inorganic Chemistry and Materials
- Photosynthetic Processes and Mechanisms
- Metalloenzymes and iron-sulfur proteins
- Organometallic Complex Synthesis and Catalysis
- Solid-state spectroscopy and crystallography
- Molecular Spectroscopy and Structure
- CO2 Reduction Techniques and Catalysts
- Catalytic Processes in Materials Science
- Synthetic Organic Chemistry Methods
- Chemical Thermodynamics and Molecular Structure
- Advanced Polymer Synthesis and Characterization
- Catalytic Cross-Coupling Reactions
- Phase Equilibria and Thermodynamics
- Sulfur-Based Synthesis Techniques
- Gene Regulatory Network Analysis
University of St Andrews
2024
KU Leuven
2017-2023
Instituto de Química Médica
2017
Universidad Autónoma de Madrid
2015
A large amount of scientific works have contributed through the years to rigorously reflect different forces leading formation hydrogen bonds, electrostatic and polarization ones being most important among them. However, we witnessed lately with emergence a new terminology, anti-electrostatic bonds (AEHBs), that seems contradict this reality. This nomenclature is used in literature describe between equally charged systems justify existence these species, despite numerous proofs showing AEHBs...
We employed our recently proposed multireference approach CASPT2/CC to calculate the quintet-triplet gaps ΔETQ of a series non-heme FeIV═O species and subsequently used these results benchmark density functional theory (DFT) as well two variants local coupled-cluster approaches (DLPNO-CCSD(T) LUCCSD(T0)). showed that current implementations method are not sufficiently accurate. DLPNO-CCSD(T) systematically overstabilizes quintet state, whereas LUCCSD(T0) overestimates triplet one. This sort...
We use a variety of computational methods to characterize and compare the hydrogen atom transfer (HAT) epoxidation reaction pathways for oxidation cyclohexene by an iron(<sc>iv</sc>)-oxo complex.
High affinity: The proton affinity (PA) of the OH group YHx compounds is always increased by noncovalent interaction (NCI) with a Lewis base (LB; see figure). This PA enhancement depends on type NCI. Weak NCIs can give rise to enhancements equal or even larger than strong NCIs. binding energies protonated species play major role in case sigma-hole interactions.
The ability of Be3 as a hydrogen bond acceptor has been explored by studying the potential complexes between this molecule and set donors (HF, HCl, HNC, HCN, H2O, HCCH). electronic structure calculations for these were carried out at MP2 CCSD(T) computational levels together with an extensive NBO, ELF, AIM, electrostatic characterization isolated system. In all complexes, Be-Be σ acts electron donor, binding energies 19 6 kJ mol-1. A comparison analogous cyclopropane:HX shows similar...
The proton affinity (PA) on the oxygen atom in silanol and siloxane derivatives is enhanced by formation of tetrel bonds with small Lewis bases [B···R3SiOH, B···R3SiOSiR3, B···R3SiOSiR3···B; B = H2O, CO, NH3, HCN, H2S; R H, Me], as shown MP2/jul-cc-pVTZ calculations. complexed systems become more basic than ether other carbon-related compounds, even pyridine some specific cases, reaching values up to 959.4 kJ/mol (H3N···H3SiOSiH3···NH3 complex). Changes PAs are directly related very large...
In the past years, there has been a discussion about how errors in density functional theory might be related to self-consistent densities obtained from different approximations. This, turn, brings up ways which we can measure such and develop metrics that assess sensitivity of calculated energies changes density. It is important realize cannot unique metric order look at this sensitivity, simultaneously needing size-extensive size-intensive metrics. study, report two are widely applicable...
The application of 1,3-divinyl-1,3-dimethyl-1,3-diferrocenyldisiloxane [(CH2═CH)FcMeSi]2O (1) as an efficient electroactive vinylsilane precursor for thiol–ene radical reactions is described. In order to determine if steric or electronic limitations due the redox-active metallocene moiety might affect bis(hydrothiolation) bifunctional vinylsilane, a model reaction was initially performed between 1 and 2-mercaptoethanol, resulting in formation newly sulfur-containing carbosiloxane 2 excellent...
The behaviour of disiloxane 1 towards a set Lewis acids (LA) and bases (LB) forming complexes through its oxygen silicon atoms, respectively, was studied at the MP2/aug′-cc-pVTZ level theory, exploring wide variety non-covalent interactions. Disiloxane is moderate electron acceptor good donor, exhibiting in latter case binding energies up to almost −100 kJ/mol with BeCl2. Cooperativity effects were also analysed by looking ternary 1:LA:LB complexes. Shorter intermolecular distances than...
The basicity of the simplest silicone, disiloxane (H3 Si-O-SiH3 ), is strongly affected by Si-O-Si angle (α). We use high-level ab initio MP2/aug'-cc-pVTZ calculations and molecular electrostatic potential (MEP) to analyze relationship between increase in reduction α. Our results clearly point out that this can be explained through MEP, as interactions oxygen from acceptors are mostly electrostatic. Furthermore, effect α on tetrel bond several Lewis bases again rationalized using MEP....
We present a mechanistic investigation of the iron-catalyzed Kumada reaction involving clusters as active species. The pioneer scientist who focused experimentally on this was Kochi, during recorded an EPR spectrum Fe(I) species that broader than expected for single-metal Fe-complex. In recent years, responsible has been isolated and characterized Fe8Me12– cluster by Neidig group. To date, its catalytic behavior studied from spectroscopic perspective but never computationally, complete...
Abstract Beryllium chemistry is typically governed by its electron deficient character, but in some compounds it can act as a base. In order to understand better the unusual basicity of Be, we have systematically explored complexes one such compound, Be(CO) 3 , towards several hydrogen bond donors HX (X=F, Cl, Br, CN, NC, CCH, OH). For all find three different minima, two bonded minima (to Be or O atoms), and weak beryllium minimum. Further characterization interactions using topological...
Multiply charged complexes bound by noncovalent interactions have been previously described in the literature, although they were mostly focused on organic and main group inorganic systems. In this work, we show that similar can also be found for organometallic systems containing transition metals deepen reasons behind existence of these species. We studied structures, binding energies, dissociation profiles gas phase a series hydrogen-bonded dimers metallocene (Ru, Co, Rh, Mn) derivatives...
Paul R. Raithby opened discussion of the paper by Maria Diaz Lopez: In pair distribution function (PDF) analysis intermolecular hydrogen bonds, what error bars would normally be acceptable for a good quality analysis? Lopez answered: uncertainties in atomic positions were ca
Odile Eisenstein opened a discussion of the paper by Stuart A. Macgregor: You have found an extended interaction between hydrogen and entire π-system arene ring. This is really interesting. involves many more electrons than localized non-covalent interactions, like o