Striking Borane Planarization in the Thermal Rearrangement (η5-C5H5)Fe(η3-B5H10)→(η5-C5H5)Fe(η5-B5H10).

In 1977 Weiss and Grimes, by means of mass spectrometry and 1H and 11B NMR spectroscopy, proposed two structures (I and II) for the ferraborane (η5-C5H5)Fe(B5H10), isoelectronic with ferrocene. In this work, by means of high-level quantum-chemical computations, we confirm the experimental structures of the two isomers with their corresponding energies, and assign the reported 1H and 11B NMR chemical shifts. A striking result from this study is the planarization (3D→2D) of the B5H10 - ligand - an unknown isolated anion, isoelectronic with aromatic cyclopentadienyl anion C5H5 - - when attached to the (η5-C5H5)Fe+ moiety, thus resulting in a more stable ferraborane isomer II.

(Pyridin-2-ylmethyl)triel Derivatives as Masked Frustrated Lewis Pairs. Interactions and CO2 -Sequestration.

The isolated (pyridin-2-ylmethyl)triel derivatives (triel=B, Al and Ga) show an intramolecular N⋅⋅⋅Tr triel bond as shown by compounds found in the Cambridge Structural Database and DFT calculations. The possibility to use them as masked frustrated Lewis pairs (mFLP) has been explored theoretically concerning their reaction with CO2 . The adduct formation proceeds in two steps. In the first one, the (pyridin-2-ylmethyl)triel derivatives break the intramolecular N⋅⋅⋅Tr bond assisted by CO2 and in the second step the adduct is formed with Tr-O and N-C covalent bonds. The corresponding energy minima and transition states (TS) of the reaction have been characterized and analyzed. The distortion/interaction model analysis of the stationary points indicates that the whole process can be divided in two parts: reorganization of the mFLP in the first steps of the reaction while the reaction with CO2 (associated to the distortion of this molecule) is more important in the formation of the final adduct. In all cases studied, the final products are more stable than the starting molecules that combine with reasonable TS energies indicating that these reactions can occur.

Towards 2D Borane Chemistry in Hexagonal Cyclic Compounds.

A comprehensive comparison between known benzene mono-substituted compounds R-Ph and the corresponding isoelectronic unknown R-cyclohexaborane(12) molecules is carried out from a geometric and electronic structure point of view, with R={H, BH2, CH3, NH2, OH, F ; AlH2, SiH3, PH2, SH, Cl ; NO2, OCH3}. We suggest new chemical names for the 2D borane compounds and analyze the geometric and electronic structure carbon vs. boron comparatives by means of HOMO-LUMO gaps, bonding schemes, electron density topological properties and predicted NMR chemical shifts. The predictions on the properties in planar hexagonal cyclic boranes may help in the design of synthesis procedures for these yet-unkown compounds.

A multi-FLP approach for CO2 capture: investigating nitrogen, boron, phosphorus and aluminium doped nanographenes and the influence of a sodium cation.

The reactivity of B3N3-doped hexa-cata-hexabenzocoronene (B3N3-NG), Al3N3-NG, B3P3-NG and Al3P3-NG, models of doped nanographenes (NGs), towards carbon dioxide was studied with density functional theory (DFT) calculations at the M06-2X/6-311++G(3df,3pd)//M06-2X/6-31+G* level of theory. The NG systems exhibit a poly-cyclic poly-frustrated Lewis pair (FLP) nature, featuring multiple Lewis acid/Lewis base pairs on their surface enabling the capture of several CO2 molecules. The capture of CO2 by these systems was investigated within two scenarios: (A) sequential capture of up to three CO2 molecules and (B) capture of CO2 molecules in the presence of a sodium cation. The resulting adducts were analyzed in terms of the activation barriers and relative stabilities. The presence of aluminium atoms changes the asynchrony of the reaction favoring the aluminium-oxygen bond and influences the regioselectivity of the multi-capture. A cooperative effect is predicted due to π-electron delocalization, with the sodium cation stabilizing the stationary points and favoring the addition of CO2 to the NGs.

Capture of CO2 by Melamine Derivatives: A DFT Study Combining the Relative Energy Gradient Method with an Interaction Energy Partitioning Scheme.

A theoretical study of the interaction between melamine and CO2 was carried out using density functional theory (DFT) with the B3LYP-D3(BJ)/aug-cc-pVTZ level of theory. The presence of anions interacting with melamine transforms the weakly bonded tetrel complexes into adducts. Thus, melamine acts as an FLP (frustrated Lewis pair) with acid groups (NHs as hydrogen bond donors) and a base group (N of the triazine ring). The application of the relative energy gradient formalism (REG) along the reaction coordinate has demonstrated that the ability of the melamine-anion systems to capture CO2 is linked to its capacity to polarize the CO2 molecule. These results have been confirmed by placing the melamine:CO2 complex in a uniform electric field with different strengths.

A theoretical study of the reaction of borata derivatives of benzene, anthracene and pentacene with CO2.

A theoretical study of the reaction between several borataacenes (1-methylboratabenzene, 9-methyl-9-borataanthracene and cis and trans diboratapentacene) and CO2 has been carried out at the M06-2X computational level. The influence of a counterion (potassium cation), the cation complexation by 18-crown-6-ether and solvent effects have been explored. The computational results predict anti/syn selectivity as found experimentally in the cis- and trans-diboratapentacene reaction with CO2 (Baker et al., J. Am. Chem. Soc., 2023, 145, 2028).

Use of 5,10-Disubstituted Dibenzoazaborines and Dibenzophosphaborines as Cyclic Supports of Frustrated Lewis Pairs for the Capture of CO2.

The reactivity of 5,10-disubstituted dibenzoazaborines and dibenzophosphaborines towards carbon dioxide was studied at the DFT, M06-2X/def2-TZVP, computational level. The profile of this reaction comprises of three stationary points: the pre-reactive complex and adduct minima and the transition state(TS) linking both minima. Initial results show that dibenzoazaborines derivatives are less suitable to form adducts with CO2 than dibenzophosphaborine systems. The influence of the basicity on the P atom and the acidity on the B center of the dibenzophosphaborine in the reaction with CO2 was also explored. Thus, an equation was developed relating the properties (acidity, basicity and boron hybridization) of the isolated dibenzophosphaborine derivatives with the adduct energy. We found that modulation of the boron acidity allows to obtain more stable adducts than the pre-reactive complexes and isolated monomers.

Sequestration of Carbon Dioxide with Frustrated Lewis Pairs Based on N-Heterocycles with Silane/Germane Groups.

Frustrated Lewis pairs (FLPs) based on nitrogen heterocycles (pyridine, pyrazole, and imidazole) with a silane or germane group in the α-position of a nitrogen atom have been considered as potential molecules to sequestrate carbon dioxide. Three stationary points have been characterized in the reaction profile: a pre-reactive complex, an adduct minimum, and the transition state connecting them. The effect of external (solvent) or internal (hydroxyl group) electric fields in the reaction profile has been considered. In both cases, it is possible to improve the kinetics and thermodynamics of the complexation of CO2 by the FLP and favor the formation of adducts.

Diborane Concatenation Leads to New Planar Boron Chemistry.

Diborane has long been realized to be analogous to ethylene in terms of its bonding MOs, both as to symmetries and splitting patterns. This naturally suggests an investigation to see whether other similar conjugated hydrocarbons manifest a similar boron-substituted and H2 supplemented borane. That is, for a conjugated hydrocarbon structure with a neighbor-paired resonance pattern, we propose to look at boranes where each carbon atom is replaced by a boron atom, and an H-atom pair is added to each double bond of the resonance structure, with one H above the molecular plane and one below. This construction of concatenated diboranes is uniformly different than that for the previously known stable boranes of 4 or more B atoms. We find from quantum-chemical computations that our so constructed polyboranes are stable. All this suggests a possible novel new chapter in borane chemistry - a chapter with some promise of understandings related to that for (alternant) conjugated hydrocarbons.

Face-Fusion of Icosahedral Boron Hydride Increases Affinity to γ-Cyclodextrin: closo,closo-[B21 H18 ]- as an Anion with Very Low Free Energy of Dehydration.

The supramolecular recognition of closo,closo-[B21 H18 ]- by cyclodextrins (CDs) has been studied in aqueous solution by isothermal titration calorimetry and nuclear magnetic resonance spectroscopy. These solution studies follow up on previous mass-spectrometric measurements and computations, which indicated the formation and stability of CD ⋅ B21 H18- complexes in the gas phase. The thermodynamic signature of solution-phase binding is exceptional, the association constant for the γ-CD complex with B21 H18- reaches 1.8×106  M-1 , which is on the same order of magnitude as the so far highest observed value for the complex between γ-CD and a metallacarborane. The nature of the intermolecular interaction is also examined by quantum-mechanical computational protocols. These suggest that the desolvation penalty, which is particularly low for the B21 H18- anion, is the decisive factor for its high binding strength. The results further suggest that the elliptical macropolyhedral boron hydride is another example of a CD binder, whose extraordinary binding affinity is driven by the chaotropic effect, which describes the intrinsic affinity of large polarizable and weakly solvated chaotropic anions to hydrophobic cavities and surfaces in aqueous solution.

Hybrid Boron-Carbon Chemistry.

The recently proved one-to-one structural equivalence between a conjugated hydrocarbon CnHm and the corresponding borane BnHm+n is applied here to hybrid systems, where each C=C double bond in the hydrocarbon is consecutively substituted by planar B(H2)B moieties from diborane(6). Quantum chemical computations with the B3LYP/cc-pVTZ method show that the structural equivalences are maintained along the substitutions, even for non-planar systems. We use as benchmark aromatic and antiaromatic (poly)cyclic conjugated hydrocarbons: cyclobutadiene, benzene, cyclooctatetraene, pentalene, benzocyclobutadiene, naphthalene and azulene. The transformation of these conjugated hydrocarbons to the corresponding boranes is analyzed from the viewpoint of geometry and electronic structure.

Complexes Between Adamantane Analogues B4X6 -X = {CH2, NH, O ; SiH2, PH, S} - and Dihydrogen, B4X6:nH2 (n = 1-4).

In this work, we study the interactions between adamantane-like structures B4X6 with X = {CH2, NH, O ; SiH2, PH, S} and dihydrogen molecules above the Boron atom, with ab initio methods based on perturbation theory (MP2/aug-cc-pVDZ). Molecular electrostatic potentials (MESP) for optimized B4X6 systems, optimized geometries, and binding energies are reported for all B4X6:nH2 (n = 1-4) complexes. All B4X6:nH2 (n = 1-4) complexes show attractive patterns, with B4O6:nH2 systems showing remarkable behavior with larger binding energies and smaller B···H2 distances as compared to the other structures with different X.

The Importance of Strain (Preorganization) in Beryllium Bonds.

In order to explore the angular strain role on the ability of Be to form strong beryllium bonds, a theoretical study of the complexes of four beryllium derivatives of orthocloso-carboranes with eight molecules (CO, N2, NCH, CNH, OH2, SH2, NH3, and PH3) acting as Lewis bases has been carried out at the G4 computational level. The results for these complexes, which contain besides Be other electron-deficient elements, such as B, have been compared with the analogous ones formed by three beryllium salts (BeCl2, CO3Be and SO4Be) with the same set of Lewis bases. The results show the presence of large and positive values of the electrostatic potential associated to the beryllium atoms in the isolated four beryllium derivatives of ortho-carboranes, evidencing an intrinsically strong acidic nature. In addition, the LUMO orbital in these systems is also associated to the beryllium atom. These features led to short intermolecular distances and large dissociation energies in the complexes of the beryllium derivatives of ortho-carboranes with the Lewis bases. Notably, as a consequence of the special framework provided by the ortho-carboranes, some of these dissociation energies are larger than the corresponding beryllium bonds in the already strongly bound SO4Be complexes, in particular for N2 and CO bases. The localized molecular orbital energy decomposition analysis (LMOEDA) shows that among the attractive terms associated with the dissociation energy, the electrostatic term is the most important one, except for the complexes with the two previously mentioned weakest bases (N2 and CO), where the polarization term dominates. Hence, these results contribute to further confirm the importance of bending on the beryllium environment leading to strong interactions through the formation of beryllium bonds.

Magnetic Properties of Co(II) Complexes with Polyhedral Carborane Ligands.

In this work we present a computational analysis of a new family of magnetic Co(II) single-ion complexes with large magnetic anisotropy based on icosahedral and octahedral carborane ligands. In particular, we extend our previous computational work on mononuclear Co(II) complexes with 1,2-(HS)2-1,2-C2B10H10 and 9,12-(HS)2-1,2-C2B10H10 icosahedral o-carborane ligands to a larger set of complexes where the Co(II) ion is doubly chelated by those ligands and by other two positional isomers belonging to the 1,2-dicarba- closo-dodecaborane family. We also describe Co(II) complexes with octahedral ligands derived from 1,2-dicarba- closo-hexaborane and study the effects of replacing a thiol group by a hydroxy group in both polyhedral geometries, as well as the influence of the position of the carbon atoms. On analysis of the results for a total of 20 complexes, our results show that carborane-based Co(II) single-ion compounds present a distorted-tetrahedral geometry, high-spin ground states, and high values for the magnetic anisotropy parameters. We point out which of these would be suitable candidates to be synthesized and used as molecular magnets.

Magnetic Properties of Mononuclear Co(II) Complexes with Carborane Ligands.

We analyze the magnetic properties of three mononuclear Co(II) coordination complexes using quantum chemical complete active space self-consistent field and N-electron valence perturbation theory approaches. The complexes are characterized by a distorted tetrahedral geometry in which the central ion is doubly chelated by the icosahedral ligands derived from 1,2-(HS)2-1,2-C2B10H10 (complex I), from 1,2-(HS)2-1,2-C2B10H10 and 9,12-(HS)2-1,2-C2B10H10 (complex II), and from 9,12-(HS)2-1,2-C2B10H10 (complex III), which are two positional isomers of dithiolated 1,2-dicarba- closo-dodecaborane (complex I). Complex I was realized experimentally recently (Tu, D.; Shao, D.; Yan, H.; Lu, C. Chem. Commun. 2016, 52, 14326) and served to validate the computational protocol employed in this work, while the remaining two proposed complexes can be considered positional isomers of I. Our calculations show that these complexes present different axial and rhombic zero-field splitting anisotropy parameters and different values of the most significant components of the g tensor. The predicted axial anisotropy D = -147.2 cm-1 for complex II is twice that observed experimentally for complex I, D = -72.8 cm-1, suggesting that this complex may be of interest for practical applications. We also analyze the temperature dependence of the magnetic susceptibility and molar magnetization for these complexes when subject to an external magnetic field. Overall, our results suggest that o-carborane-incorporated Co(II) complexes are worthwhile candidates for experimental exploration as single-ion molecular magnets.

Ab initio quantum-chemical computations of the absorption cross sections of HgX2 and HgXY (X, Y = Cl, Br, and I): molecules of interest in the Earth's atmosphere.

The electronic-structure properties of the low-lying electronic states and the absorption cross sections (σ(E)) of mercury halides HgCl2, HgBr2, HgI2, HgBrCl, HgClI, and HgBrI have been determined within the UV-vis spectrum range (170 nm ≤ λphoton ≤ 600 nm) by means of the DKH3-MS-CASPT2/SO-RASSI quantum-chemical methodology (with the ANO-RCC basis set) and a semi-classical computational strategy based on nuclear sampling for simulating the band shapes. Computed band energies show a good agreement with the available experimental data for HgX2 with errors around 0.1-0.2 eV; theoretical and σ(E) are within the same order of magnitude. For the mixed HgXY compounds, the present computed data allow us to interpret previously proposed absorption bands estimated from the spectra of the parent molecules HgX2 and HgY2, measured in methanol solution. The analyses performed on the excited-state electronic structure and its changes around the Franck-Condon region provide a rationale on the singlet-triplet mixing of the absorption bands and the heavy-atom effect of the Hg compounds. Furthermore, the present benchmark of HgX2 and HgXY absorption σ values together with the previous benchmark of the electronic-structure properties of HgBr2 [see S. P. Sitkiewicz, et al., J. Chem. Phys., 2016, 145, 244304] has been helpful to set up a methodological and computational protocol which shall be used for predicting the atmospheric absorption and photolysis properties of several Hg compounds present in the atmospheric cycle of Hg.

Binary twinned-icosahedral [B21H18]- interacts with cyclodextrins as a precedent for its complexation with other organic motifs.

The weakly coordinating binary macropolyhedral anion closo,closo-[B21H18]- (B21; D3h symmetry) has been synthesized using a simplified strategy compared to that in the literature. While gas-phase complexes of B21 with ß- and γ-cyclodextrin (CD) were detected using ESI FT-ICR spectrometric measurements, α-CD did not bind to the B21 guest. This spectroscopic evidence has been interpreted using quantum-chemical computations, showing that ß- and γ-CD are able to interact with B21 due to their larger cavities, in contrast to the smaller α-CD. The hydridic B-H vectors of the B21 anion interact with K+ counterions and, via dihydrogen bonding, also with the partially positively charged hydrogens of the CD sugar units in the modeled ß- and γ-CD complexes. In summary, it has been shown by combined spectrometric/computational analysis that macropolyhedral boron hydride anions with two counterions can form stable complexes with ß- and γ-CD in the gas phase, offering a new perspective for the future investigation of this remarkable anion in the areas of supramolecular and medicinal chemistries.

Reactivity of a model of B3P3-doped nanographene with up to three CO2 molecules.

The reactivity of a B3P3-doped hexa-cata-hexabenzocoronene, as a model of nanographene (B3P3-NG), towards carbon dioxide was studied at the DFT M06-2X/6-311++G(3df,3pd)//M06-2X/6-31+G* level of theory. This compound can be classified as a poly-cyclic poly-Frustrated Lewis Pair (FLP) system, as it presents more than one Lewis Acid/Lewis Base pair on its surface, making the capture of several carbon dioxide molecules possible. Two scenarios were considered to fully characterize the capture of CO2 by this multi-FLP system: (i) fixation of three CO2 molecules sequentially one by one; and (ii) simultaneous contact of three CO2 molecules with the B3P3-NG surface. The resulting adducts were analyzed as function of activation barriers and the relative stability of the CO2 capture. A cooperativity effect due to the π-delocalization of the hexa-cata-hexabenzocoronene is observed. The fixation of a CO2 molecule modifies the electronic properties. It enhances the capture of additional CO2 molecules by changing the acidy and basicity of the rest of the boron and phosphorus atoms in the B3P3-NG system.

Two Shared Icosahedral Metallacarboranes through Iron: A Joint Experimental and Theoretical Refinement of Mössbauer Spectrum in [Fe(1,2-C2B9H11)2]Cs.

Mössbauer and X-ray photoelectron spectroscopies (XPS) are complemented with high-level quantum-chemical computations in the study of the geometric and electronic structure of the paramagnetic salt of the metallacarborane sandwich complex [Fe(1,2-C2B9H11)2]Cs = FeSanCs. Experimental 57Fe isomer shifts and quadrupole splitting parameters are compared with the theoretical prediction, with good agreement. The appearance of two sets of Cs(3d) doublets in the XPS spectrum, separated by 2 eV, indicates that Cs has two different chemical environments due to ease of the Cs(+) cation moving around the sandwich complex with low-energy barriers, as confirmed by quantum-chemical computations. Several minimum-energy geometries of the FeSanCs structure with the corresponding energies and Mössbauer parameters are discussed, in particular the atomic charges and spin population and the surroundings of the Fe atom in the complex. The Mössbauer spectra were taken at different temperatures showing the presence of a low-spin Fe atom with S = 1/2 and thus confirming a paramagnetic FeIII species.

Experimental and Computational Studies on the Gas-Phase Acidity of 5,5-Dialkyl Barbituric Acids.

The gas phase acidities (GA) of 5,5-alkylbarbituric acids have been experimentally determined by electrospray ionization-triple quadrupole (ESI-TQ) mass spectrometry and by using the extended kinetic Cooks method (EKCM). The GAs of C-H (1330.9 ± 10.0 kJ mol-1) and N-H (1361.5 ± 10.5 kJ mol-1) deprotonated sites of bifunctional barbituric acid were determined from the selective production of their corresponding heterodimers. The GA value in the N-H site was confirmed by measuring the GAs of 5,5-dimethyl- and 5,5-diethyl barbituric acids (∼1368 kJ mol-1). The experimental results have been rationalized and discussed with the support of quantum chemical calculations with Gaussian-n (G3 and G4) composite methods, which confirmed the excellent consistency of the results.