Josep M. Luis

Observation of Fe(V)=O using variable-temperature mass spectrometry and its enzyme-like C–H and C=C oxidation reactions

Oxo-transfer chemistry mediated by iron underpins many biological processes and today is emerging as synthetically very important for the catalytic oxidation of C-H and C=C moieties that are hard to activate conventionally. Despite the vast amount of research in this area, experimental characterization of the reactive species under catalytic conditions is very limited, although a Fe(V)=O moiety was postulated. Here we show, using variable-temperature mass spectrometry, the generation of a Fe(V)=O species within a synthetic non-haem complex at -40 °C and its reaction with an olefin. Also, with isotopic labelling we were able both to follow oxygen-atom transfer from H(2)O(2)/H(2)O through Fe(V)=O to the products and to probe the reactivity as a function of temperature. This study pioneers the implementation of variable-temperature mass spectrometry to investigate reactive intermediates.

Basis set and electron correlation effects on ab initio electronic and vibrational nonlinear optical properties of conjugated organic molecules

We have studied how the calculation of electronic and vibrational contributions to nonlinear optical properties of three representative π-conjugated organic molecules is affected by the choice of basis set and the inclusion of electron correlation effects. The 6-31G basis does not always provide even qualitative accuracy. For semiquantitative accuracy a 6-31+G(d) basis is sufficient. Although, as compared to QCISD, a second-order Moller–Plesset (MP2) treatment often yields a substantial fraction of the electron correlation contribution, our MP2 results for the separate electronic and vibrational terms are not consistently of semiquantitative accuracy. Nevertheless, at the MP2 level the ratio between the vibrational and electronic contributions is satisfactorily reproduced.

Linear and Nonlinear Optical Properties of (60)Fullerene Derivatives

Using a wide variety of quantum-chemical methods we have analyzed in detail the linear and non-linear optical properties of [60]fullerene-chromophore dyads of different electron-donor character. The dyads are composed of [60]fullerene covalently linked with 2,1,3-benzothiadiazole and carbazole derivatives. Linear scaling calculations of molecular (hyper)polarizabilities were performed using wave function theory as well as density functional theory (DFT). Within the former approach, we used both semiempirical (PM3) and ab initio (Hartree-Fock and second-order Møller-Plesset perturbation theory) methods. Within the latter approach only the recently proposed long-range (LRC) schemes successfully avoid a large overshoot in the value obtained for the first hyperpolarizability (β). Calculations on model fullerene derivatives establish a connection between this overshoot and the electron-donating capability of the substituent. Substitution of 2,1,3-benzothiadiazole by the triphenylamine group significantly increases the electronic first and second hyperpolarizabilities as well as the two-photon absorption cross section. For [60]fullerene-chromophore dyads we have, additionally, observed that the double harmonic vibrational contribution to the static beta is much larger than its electronic counterpart. The same is true for the dc-Pockels β as compared to the static electronic value, although the vibrational term is reduced in magnitude; for the intensity-dependent refractive index the vibrational and electronic terms are comparable. A nuclear relaxation treatment of vibrational anharmonicity for a model fulleropyrrolidine molecule yields a first-order contribution that is substantially more important than the double harmonic term for the static β.

Electronic Effects on Single‐Site Iron Catalysts for Water Oxidation

Getting in tune: Systematic tuning of the electronic properties of modular non-heme iron coordination complexes can be used to extract important information on the reaction mechanism and intermediates, which, in turn, help to explain the activity of these systems as water oxidation catalysts.

Olefin-Dependent Discrimination between Two Nonheme HO-FeV=O Tautomeric Species in Catalytic H2O2 Epoxidations

Wet oxygenase models: Unprecedented high levels of water incorporation into products (up to 75%) is observed in epoxidation reactions with H(2)O(2) by a bioinspired nonheme iron catalyst. A surprising substrate-dependent incorporation of water is observed, and is proposed to arise from fast equilibrium between two high-valent HO-Fe(V)=O isomeric species exhibiting different reactivity.

A systematic and feasible method for computing nuclear contributions to electrical properties of polyatomic molecules

An analytic method to evaluate nuclear contributions to electrical properties of polyatomic molecules is presented. Such contributions control changes induced by an electric field on equilibrium geometry (nuclear relaxation contribution) and vibrational motion (vibrational contribution) of a molecular system. Expressions to compute the nuclear contributions have been derived from a power series expansion of the potential energy. These contributions to the electrical properties are given in terms of energy derivatives with respect to normal coordinates, electric field intensity or both. Only one calculation of such derivatives at the field-free equilibrium geometry is required. To show the useful efficiency of the analytical evaluation of electrical properties (the so-called AEEP method), results for calculations on water and pyridine at the SCF/TZ2P and the MP2/TZ2P levels of theory are reported. The results obtained are compared with previous theoretical calculations and with experimental values.

Finite field treatment of vibrational polarizabilities and hyperpolarizabilities: On the role of the Eckart conditions, their implementation, and their use in characterizing key vibrations

In the finite field (FF) treatment of vibrational polarizabilities and hyperpolarizabilities, the field-free Eckart conditions must be enforced in order to prevent molecular reorientation during geometry optimization. These conditions are implemented for the first time. Our procedure facilities identification of field-induced internal coordinates that make the major contribution to the vibrational properties. Using only two of these coordinates, quantitative accuracy for nuclear relaxation polarizabilities and hyperpolarizabilities is achieved in π-conjugated systems. From these two coordinates a single most efficient natural conjugation coordinate (NCC) can be extracted. The limitations of this one coordinate approach are discussed. It is shown that the Eckart conditions can lead to an isotope effect that is comparable to the isotope effect on zero-point vibrational averaging, but with a different mass-dependence.

The role of aromaticity in determining the molecular structure and reactivity of (endohedral metallo)fullerenes

The encapsulation of metal clusters in endohedral metallofullerenes (EMFs) takes place in cages that in most cases are far from being the most stable isomer in the corresponding hollow fullerenes. There exist several possible explanations for the choice of the hosting cages in EMFs, although the final reasons are actually not totally well understood. Moreover, the reactivity and regioselectivity of (endohedral metallo)fullerenes have in the past decade been shown to be generally dependent on a number of factors, such as the size of the fullerene cage, the type of cluster that is being encapsulated, and the number of electrons that are transferred formally from the cluster to the fullerene cage. Different rationalizations of the observed trends had been proposed, based on bond lengths, pyramidalization angles, shape and energies of (un)occupied orbitals, deformation energies of the cages, or separation distances between the pentagon rings. Recently, in our group we proposed that the quest for the maximum aromaticity (maximum aromaticity criterion) determines the most suitable hosting carbon cage for a given metallic cluster (i.e. EMF stabilization), including those cases where the IPR rule is not fulfilled. Moreover, we suggested that local aromaticity plays a determining role in the reactivity of EMFs, which can be used as a criterion for understanding and predicting the regioselectivity of different reactions such as Diels-Alder cycloadditions or Bingel-Hirsch reactions. This review highlights different aspects of the aromaticity of fullerenes and EMFs, starting from how this can be measured and ending by how it can be used to rationalize and predict their molecular structure and reactivity.

The Mechanism of Stereospecific CH Oxidation by Fe(Pytacn) Complexes: Bioinspired Non‐Heme Iron Catalysts Containing cis‐Labile Exchangeable Sites

A detailed mechanistic study of the hydroxylation of alkane C-H bonds using H2O2 by a family of mononuclear non heme iron catalysts with the formula [Fe(II)(CF3SO3)2(L)] is described, in which L is a tetradentate ligand containing a triazacyclononane tripod and a pyridine ring bearing different substituents at the α and γ positions, which tune the electronic or steric properties of the corresponding iron complexes. Two inequivalent cis-labile exchangeable sites, occupied by triflate ions, complete the octahedral iron coordination sphere. The C-H hydroxylation mediated by this family of complexes takes place with retention of configuration. Oxygen atoms from water are incorporated into hydroxylated products and the extent of this incorporation depends in a systematic manner on the nature of the catalyst, and the substrate. Mechanistic probes and isotopic analyses, in combination with detailed density functional theory (DFT) calculations, provide strong evidence that C-H hydroxylation is performed by highly electrophilic [Fe(V)(O)(OH)L] species through a concerted asynchronous mechanism, involving homolytic breakage of the C-H bond, followed by rebound of the hydroxyl ligand. The [Fe(V)(O)(OH)L] species can exist in two tautomeric forms, differing in the position of oxo and hydroxide ligands. Isotopic-labeling analysis shows that the relative reactivities of the two tautomeric forms are sensitively affected by the α substituent of the pyridine, and this reactivity behavior is rationalized by computational methods.

Determination of vibrational polarizabilities and hyperpolarizabilities using field-induced coordinates

An analytical set of field-induced coordinates (FICs) is defined. It is shown that, instead of 3N−6 normal coordinates, a relatively small number of FICs is sufficient to describe the vibrational polarizability and hyperpolarizabilities due to nuclear relaxation. The fact that the number of FICs does not depend upon the size of the molecule leads to computational advantages. A method is provided for separating anharmonic contributions from harmonic contributions as well as effective mechanical from electrical anharmonicity. Hartree–Fock calculations on a dozen representative conjugated molecules illustrate the procedures and indicate that anharmonicity can be very important. Other potential applications including the determination of zero-point vibrational averaging corrections are noted.