On the Role of Symmetry in Vibrational Strong Coupling: The Case of Charge-Transfer Complexation

It is well known that symmetry plays a key role in chemical reactivity. Here we explore its role in vibrational strong coupling (VSC) for a charge-transfer (CT) complexation reaction. By studying the trimethylated-benzene–I₂ CT complex, we find that VSC induces large changes in the equilibrium constant K_DA of the CT complex, reflecting modifications in the ΔG° value of the reaction. Furthermore, by tuning the microfluidic cavity modes to the different IR vibrations of the trimethylated benzene, ΔG° either increases or decreases depending only on the symmetry of the normal mode that is coupled. This result reveals the critical role of symmetry in VSC and, in turn, provides an explanation for why the magnitude of chemical changes induced by VSC are much greater than the Rabi splitting, that is, the energy perturbation caused by VSC. These findings further confirm that VSC is powerful and versatile tool for the molecular sciences.     

Activation of Strong Boron–Fluorine and Silicon–Fluorine σ‐Bonds: Theoretical Understanding and Prediction

The oxidative addition of BF₃ to a platinum(0) bis(phosphine) complex [Pt(PMe₃)₂] ( 1 ) was investigated by density functional calculations. Both the cis and trans pathways for the oxidative addition of BF₃ to 1 are endergonic (ΔG°=26.8 and 35.7 kcal mol^?1, respectively) and require large Gibbs activation energies (ΔG°^≠=56.3 and 38.9 kcal mol^?1, respectively). A second borane plays crucial roles in accelerating the activation; the trans oxidative addition of BF₃ to 1 in the presence of a second BF₃ molecule occurs with ΔG°^≠ and ΔG° values of 10.1 and ?4.7 kcal mol^?1, respectively. ΔG°^≠ becomes very small and ΔG° becomes negative. A charge transfer (CT), F→BF₃, occurs from the dissociating fluoride to the second non‐coordinated BF₃. This CT interaction stabilizes both the transition state and the product. The B?F σ‐bond cleavage of BF₂Ar^F (Ar^F=3,5‐bis(trifluoromethyl)phenyl) and the B?Cl σ‐bond cleavage of BCl₃ by 1 are accelerated by the participation of the second borane. The calculations predict that trans oxidative addition of SiF₄ to 1 easily occurs in the presence of a second SiF₄ molecule via the formation of a hypervalent Si species.     

Kinetics and mechanism of diels-alder additions of tetracyanoethylene to anthracene derivatives—I : Substituent effects

The rates of addition of tetracyanoethylene to a number of 9- and 9,10-substituted anthracenes have been measured spectrophotometrically in solvent CCl₄. Substituent effects correlated well using the extended form of the Hammett equation. The importance of steric effects on the reaction was assessed by a systematic variation of the components of the data used in the above correlation.Activation parameters (ΔG_exp^≠, etc.) and the corresponding overall thermodynamic parameters for adduct formation (ΔG_ad°, etc.) were evaluated. ΔG_exp^≠ was found to be linearly related to ΔG_c°, the free energy of formation of the intermediate complex which confirms the role of the latter as a true reaction intermediate. From correlations between ΔG_exp^≠ and ΔG_ad°, an “early” transition state is suggested. The above thermodynamic and activation data enable detailed reaction profiles to be drawn.     

A Thermodynamic and Kinetic Insight into the Pathways Leading to a Highly Functionalized Ketenimine: A Computational Study

All steps of two mechanistic pathways for the synthesized ketenimine through a multicomponent reaction between cyclohexyl isocyanide 1 and acetylen ester 2 in the presence of CH‐acid 3 have been thermodynamically and kinetically evaluated. Intrinsic reaction coordinate calculations were performed for the optimized structures to verify the connectivity of all transition states with reactants and products. The kinetic data showed that the step 1 of the two proposed mechanisms was a rate‐determining step. Also, activation (ΔG^?, ΔH^?, ΔS^?) and thermodynamic (ΔG°, ΔH°, ΔS°) parameters confirmed that the second mechanism for generation product 4b was favored energetically. In addition, the single‐point ¹H and ¹³C NMR (GIAO) chemical shift calculations showed that the product obtained from the approval pathway was according to the experimental data.     

Kinetic and thermodynamic properties of the aerial oxidation of hydroquinone in developer solutions

The aerial oxidation kinetics of hydroquinone in a freshly prepared developer solution at different temperatures and pHs has been studied. The activation parameters, Ea, ΔG# , ΔS# , ΔH# and enthalpy of formation of activated complex, ΔHfo(X# ), are determined. The large negative value of free energy of activation ΔG# proves that hydroquinone extremely tends to be oxidized by air at optimum temperature (20℃) and optimum pH (10.5) and converts to the activated complex semiquinone. It was also found that if the pH of the developer solution is increased from 9.3 to 10.5 the reaction rate will increase by a factor of 2.     

Solvation and temperature effect on the charge-transfer complex between 2-amino-4-picoline with 2,5-dihydroxy-p-benzoquinone

The charge-transfer (CT) complex between the donor 2-amino-4-picoline (2A4P) and the acceptor 2,5-dihydroxy-p-benzoquinone (DHBQ) was studied spectrophotometrically in different polar and non-polar solvents. The molecular composition of the complex, in all solvents, was determined by Job's method of continuous variation and photometric titrations to be 1:1. Benesi–Hildebrand equation has been applied to estimate the formation constant (K _CT) and molecular extinction coefficient (ε) of the formed complex. The variation in K _CT was rationalised based on Taft–Kamlet and electric permittivity parameters of the used solvents. Thermodynamic parameters ΔH°, ΔG° and ΔS° were estimated, they were all negative so the studied complex is reasonably stable and exothermic in nature. In addition, the thermodynamic properties were observed to be sensitive to the nature of the solvent. Moreover, the solid 1:1 CT complex between 2A4P and DHBQ was isolated and characterised using elemental analysis, FTIR and ¹H NMR measurements.     

Kinetics and mechanism of decomposition of intermediate complex during oxidation of pectate polysaccharide by potassium permanganate in alkaline solutions

The kinetics of decomposition of an [Pect·Mn^VIO₄^2?] intermediate complex have been investigated spectrophotometrically at various temperatures of 15–30°C and a constant ionic strength of 0.1 mol dm^?3. The decomposition reaction was found to be first‐order in the intermediate concentration. The results showed that the rate of reaction was base‐catalyzed. The kinetic parameters have been evaluated and found to be ΔS^≠ = ? 190.06 ± 9.84 J mol^?1 K^?1, ΔH^≠ = 19.75 ± 0.57 kJ mol^?1, and ΔG^≠ = 76.39 ± 3.50 kJ mol^?1, respectively. A reaction mechanism consistent with the results is discussed. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 35: 67–72, 2003     

A Nexus between Theory and Experiment: Non‐Empirical Quantum Mechanical Computational Methodology Applied to Cucurbit[n]uril⋅Guest Binding Interactions

A training set of eleven X‐ray structures determined for biomimetic complexes between cucurbit[n]uril (CB[7 or 8]) hosts and adamantane‐/diamantane ammonium/aminium guests were studied with DFT‐D3 quantum mechanical computational methods to afford ΔG_calcd binding energies. A novel feature of this work is that the fidelity of the BLYP‐D3/def2‐TZVPP choice of DFT functional was proven by comparison with more accurate methods. For the first time, the CB[n] ? guest complex binding energy subcomponents [for example, ΔE_dispersion, ΔE_{electrostatic}, ΔG_solvation, binding entropy (?TΔS), and induced fit E_{deformation(host)}, E_{deformation(guest)}] were calculated. Only a few weeks of computation time per complex were required by using this protocol. The deformation (stiffness) and solvation properties (with emphasis on cavity desolvation) of cucurbit[n]uril (n=5, 6, 7, 8) isolated host molecules were also explored by means of the DFT‐D3 method. A high ρ²=0.84 correlation coefficient between ΔG_exptl and ΔG_calcd was achieved without any scaling of the calculated terms (at 298 K). This linear dependence was utilized for ΔG_calcd predictions of new complexes. The nature of binding, including the role of high energy water molecules, was also studied. The utility of introduction of tethered [‐(CH₂)_nNH₃]⁺ amino loops attached to N,N‐dimethyl‐adamantane‐1‐amine and N,N,N′,N′‐tetramethyl diamantane‐4,9‐diamine skeletons (both from an experimental and a theoretical perspective) is presented here as a promising tool for the achievement of new ultra‐high binding guests to CB[7] hosts. Predictions of not yet measured equilibrium constants are presented herein.     

Chemical exchange in novel spirobicyclic zwitterionic Janovsky complexes using dynamic 1H NMR spectroscopy

Highly coloured Janovsky complexes have been known for over 120 years, being used in many colourimetric analytical procedures. In this present study, two novel and stable nitrocyclohexadienyl spirobicyclic, zwitterionic Janovsky anionic hydantoin σ‐complexes, rac‐1,3‐diisopropyl‐6‐nitro‐2,4‐dioxo‐1,3‐diazaspiro[4.5]deca‐6,9‐dien‐8‐ylideneazinate, ammonium internal salt (1) and 1,3‐diisopropyl‐2,4‐dioxo‐1,3‐diazaspiro[4.5]deca‐6,9‐dien‐8‐ylideneazinate, ammonium internal salt (2) have been prepared and characterised by NMR, electrospray ionization mass spectrometry (ESI‐MS) and UV/visible methods. For the p‐mononitro‐substituted complex (2), we discovered chemical exchange behaviour using 1D saturation transfer and 2D exchange spectroscopy (EXSY) ¹H NMR techniques. The coalescence temperature was determined to be 62 °C in d₃‐acetonitrile. Analysis of these data provided a Gibbs free energy of activation, ΔG ?, of + 67 kJ mole^?1, a rate constant, k, coalescence of 220 Hz and an equilibrium constant, K_eqm, of 0.98 as estimates of the exchange process in this solvent. Of the two mechanisms proposed for this fluxional behaviour, ring opening to a substituted benzene or proton exchange, a further theoretical modelling study of 1D ¹H NMR spectra was able to confirm that simple proton exchange between the two nitrogen sites of the hydantoin ring provided an accurate simulation of the observed experimental evidence. Interestingly, the o,p‐dinitro‐substituted complex (1) did not show any chemical exchange behaviour up to 150 °C in d₃‐acetonitrile (to 75 °C) and d₆‐dimethyl sulfoxide (DMSO). Molecular modelling at the MM2 level suggests that steric collisions of an N‐acyl isopropyl substituent of the hydantoin ring with the ortho‐nitro group of the spirofused cyclohexadienyl ring prevents the proposed proton exchange mechanism occurring in this case. Copyright © 2008 Crown in the right of Canada. Published by John Wiley & Sons, Ltd     

Influence of solvent structure on the aquation of K‐chloro(diethylenetriamine)(ethylenediamine) cobalt(III) ion in water and mixed aqueous solvents

The aquation of K‐[Co(dien)(en)Cl]²⁺ was followed spectrophotometrically within the temperature range (40–60°C) in water, water–isopropyl alcohol, and water–tert‐butyl alcohol media of varying solvent composition up to 50 and 60 vol% of the organic solvent component respectively. The nonlinear plot of log k vs. D^?1_s was attributed to the differential solvation of the initial and transition states. The variation of ΔH^≠, ΔS^≠, and ΔG^≠ with the mole fraction of the organic component was analyzed and discussed. The isokinetic temperatures were found to be 330 and 317 K for water–isopropyl alcohol and water–tert‐butly alcohol mixtures respectively, indicating that the aquation reaction is entropy controlled. The application of free energy cycle at 25°C for the aquation reaction in both co‐solvents suggests that the transition state is more stable than the initial one. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 34: 1–6, 2002     

Synthesis and Characterization of Acetylene‐Linked Bisphenalenyl and Metallic‐Like Behavior in Its Charge‐Transfer Complex

We prepared and isolated a phenalenyl‐based neutral hydrocarbon ( 1 b ) with a biradical index of 14 %, as well as its charge‐transfer (CT) complex 1 b –F₄‐TCNQ. The crystal structure and the small HOMO–LUMO gap assessed by electrochemical and optical methods support the singlet‐biradical contribution to the ground state of the neutral 1 b . This biradical character suggests that 1 b has the electronic structure of phenalenyl radicals coupled weakly through an acetylene linker, that is, some independence of the two phenalenyl moieties. The monocationic species 1 b^{. +} was obtained by reaction with the organic electron acceptor F₄‐TCNQ. The cationic species has a small disproportionation energy ΔE for the reaction 2× 1 b^{. +}? 1 b + 1 b ²⁺, which presumably originates from the independence of the phenalenyl moieties. The small ΔE led to a small on‐site Coulombic repulsion U_eff=0.61 eV in the CT complex. Moreover, a very effective orbital overlap of the phenalenyl rings between molecules afforded a relatively large transfer integral t=0.09 eV. The small U_eff/4t ratio (=1.7) resulted in a metallic‐like conductive behavior at around room temperature. Below 280 K, the CT complex showed a transition into a semiconductive state as a result of bond formation between phenalenyl and F₄‐TCNQ carbon atoms.     

3‐[4′‐(Diethylboryl)phenyl]pyridine: Exclusive Crystallization of the Cyclic Tetramer

The crystallization of 3‐[4′‐(diethylboryl)phenyl]pyridine ( 1 ), which formed a mixture of oligomers in solution with the cyclic trimer as a major component, in acetone at 0 °C afforded a cyclic tetramer that co‐crystallized with solvent molecules. Similarly, solutions of compound 1 in toluene at 10 °C and in benzene at 8 °C furnished the cyclic tetramer with the incorporation of toluene and benzene molecules, respectively, thus suggesting that the cyclic tetramer was the minor component. ¹³C CP/MAS NMR spectroscopy of precipitates of compound 1 suggested that precipitation from acetone and toluene each afforded mixtures of the cyclic trimer and the cyclic tetramer, whereas precipitation from benzene exclusively furnished the cyclic tetramer. Therefore, it appeared that crystallization readily shifted the equilibrium towards the cyclic tetramer in benzene. The thermodynamic parameters for the equilibrium between these two oligomers in [D₆]benzene, as determined from a van′t Hoff plot, were ΔH°=?8.8 kcal mol^?1 and ΔS°=?23.7 cal mol^?1 K^?1, which were coincident with previously reported calculations and observations.     

Thermal Behavior of N,N＇Bis[N-（2,2,2-trinitroethyl）-N-nitro]ethylenediamine

The thermal behavior and kinetic parameters of the exothermic decomposition reaction of N‐N‐bis[N‐(2,2,2‐tri‐nitroethyl)‐N‐nitro]ethylenediamine in a temperature‐programmed mode have been investigated by means of differential scanning calorimetry (DSC). The results show that kinetic model function in differential form, apparent activation energy E_a and pre‐exponential factor A of this reaction are 3(1 ‐α)^2/3, 203.67 kJ·mol^?1 and 10^20.61s^?1, respectively. The critical temperature of thermal explosion of the compound is 182.2 °C. The values of ΔS^≠ ΔH^≠ and ΔG^≠ of this reaction are 143.3 J·mol^?1·K^?1, 199.5 kJ·mol^?1 and 135.5 kJ·mol^?1, respectively.     

An easy way to achieve three‐dimensional metal–organic coordination polymers: synthesis and crystal structure of dizinc diisophthalate bis‐dimethylsulfoxide monohydrate: [Zn2(ip)4(DMSO)2(H2O)·3 DMSO]n

An easy way of producing three‐dimensional metal–organic coordination polymers involving zinc(II) benzene‐dicarboxylates is reported. The reaction of zinc oxide with benzene dicarboxylic acids in water yielded the expected hydrated zinc dicarboxylates. These zinc compounds were then suspended in dimethylsulfoxide and heated to above 100 °C for a couple of hours; the solutions were allowed after filtration to cool down to eventually deliver crystalline compounds displaying complex zeotype structures. The crystal structure of the title compound, [Zn₂(ip)₄(DMSO)₂(H₂O)·3 DMSO]_n (ipH₂ = isophthalic acid = 1,3‐benzenedicarboxylic acid, DMSO = dimethylsulfoxide), is reported for the first time and shows a three‐dimensional network where octahedrally and tetrahedrally coordinated zinc atoms (present in a 1:1 ratio) are linked by bridging isophthalate ligands. The complex coordination network exhibits a remarkable channel structure along the z‐axis. The related zinc terephthalate–DMSO complex was similarly prepared and the crystal structure determination revealed an already documented zeotypic structure: [{Zn₄(OH)₂(tp)₃(DMSO)₄} 2H₂O]_n (tpH₂ = terephthalic acid = 1,4‐benzenedicarboxylic acid). Weak interactions as well as hydrogen bonds involving water molecules and carboxy groups play a major role in the formation of these complex three‐dimensional networks. In comparison, the zinc 1,2‐benzene‐dicarboxylate–DMSO complex could not be isolated, even under more drastic conditions. The higher symmetry of the coordination network found in the zinc terephthalate–DMSO complexes was incidentally corroborated by ¹³C CP/MAS spectroscopy. Copyright © 2007 John Wiley & Sons, Ltd.     

Effects of Isomerization on the Measured Thermochemical Properties of Deprotonated Glycine/Protic‐Solvent Clusters

The thermochemical properties associated with the formation of an isomeric distribution of ROH???NH₂CH₂COO^? clusters (R=H, CH₃, C₂H₅) are measured by using high‐pressure mass spectrometry. A comparison of the measured properties with calculated values provides new insights into the thermochemical effects arising from the isomeric nature of this clustering system. When the distribution of isomers is correctly accounted for, the measured values of ΔH°, ΔS°, and ΔG°₂₉₈ consistently agree, to a very high degree of accuracy, with those predicted by MP2(full)/6‐311++G(d,p)//B3LYP/6‐311++G(d,p) calculations.     

Optimal scaling factors for CM1 and CM3 atomic charges in RM1-based aqueous simulations

Scaling factors for atomic charges derived from the RM1 semiempirical quantum mechanical wavefunction in conjunction with CM1 and CM3 charge models have been optimized by minimizing errors in absolute free energies of hydration, ΔG_hyd, for a set of 40 molecules. Monte Carlo statistical mechanics simulations and free energy perturbation theory were used to annihilate the solutes in gas and in a box of TIP4P water molecules. Lennard–Jones parameters from the optimized potentials for liquid simulations‐all atom (OPLS–AA) force field were utilized for the organic compounds. Optimal charge scaling factors have been determined as 1.11 and 1.14 for the CM1R and CM3R methods, respectively, and the corresponding unsigned average errors in ΔG_hyd relative to experiment were 2.05 and 1.89 kcal/mol. Computed errors in aniline and two derivatives were particularly large for RM1 and their removal from the data set lowered the overall errors to 1.61 and 1.75 kcal/mol for CM1R and CM3R. Comparisons are made to the AM1 method which yielded total errors in ΔG_hyd of 1.50 and 1.64 kcal/mol for CM1A*1.14 and CM3A*1.15, respectively. This work is motivated by the need for a highly efficient yet accurate quantum mechanical (QM) method to study condensed‐phase and enzymatic chemical reactions via mixed QM and molecular mechanical (QM/MM) simulations. As an initial test, the Menshutkin reaction between NH₃ and CH₃Cl in water was computed using a RM1/TIP4P‐Ew/CM3R procedure and the resultant ΔG^?, ΔG_rxn, and geometries were in reasonable accord with other computational methods; however, some potentially serious shortcomings in RM1 are discussed. © 2011 Wiley Periodicals, Inc. J Comput Chem, 2011     

Standard states and standard adsorption gibbs energy of substances at electrode interfaces

The physical meaning of ΔG°_ad is discussed in terms of choice of standard states, form of the isotherm equation, true adsorption equilibrium reaction and contributions from interactions in the solution bulk. It is shown that the quantitative value of ΔG°_ad may be misleading if the above factors are not taken into account properly. The particular case of thiourea adsorption on Hg is discussed in detail. It is recommended that surface and bulk concentrations are expressed as mole fractions whenever possible so as to minimize problems of ΔG°_ad interconversion among different isotherms.     

Comparison between ab Initio and Modified INDO-MO Calculations of N20

Both STO-3G ab initio and s-p separation-type-modified INDO semiempirical methods were applied to molecular-orbital calculation of the N₂₀ molecule. From these two methods, the optimized bond distances between the nearest N atoms (d_n-n) and the most calculated thermodynamic data are close to each other. The positive values of ΔH_a° and ΔG_a° for the atomization reaction in this work prove that N₂₀ is stable. In contrast to conventional INDO and MINDO/3, but similar to former AMI and MNDO calculations, both ΔH_r° and ΔG_r° are positive in the formation reaction, which indicates that N₂₀ belongs to the category of high-energy molecules.     

New insight into the substituent effects on the hydrolytic deamination of saturated and unsaturated cytosine

Ab initio calculations were carried out to understand the effect of electron donating groups (EDG) and electron withdrawing groups (EWG) at the C5 position of cytosine (Cyt) and saturated cytosine (H₂Cyt) of the deamination reaction. Geometries of the reactants, transition states, intermediates, and products were fully optimized at the B3LYP/6-31G(d,p) level in the gas phase as this level of theory has been found to agree very well with G3 theories. Activation energies, enthalpies, and Gibbs energies of activation along with the thermodynamic properties (ΔE, ΔH, and ΔG) of each reaction were calculated. A plot of the Gibbs energies of activation (ΔG^‡) for C5 substituted Cyt and H₂Cyt against the Hammett σ-constants reveal a good linear relationship. In general, both EDG and EWG substituents at the C5 position in Cyt results in higher ΔG^‡ and lower σ values compared to those of H₂Cyt deamination reactions. C5 alkyl substituents ( H,  CH₃,  CH₂CH₃,  CH₂CH₂CH₃) increase ΔG^‡ values for Cyt, while the same substituents decrease ΔG^‡ values for H₂Cyt which is likely due to steric effects. However, the Hammett σ-constants were found to decrease at the C5 position of cytosine (Cyt) and saturated cytosine (H2Cyt) on the deamination reaction. Both ΔG^‡ and σ values decrease for the substituents Cl and Br in the Cyt reaction, while ΔG^‡ values increase and σ decrease in the H₂Cyt reaction. This may be due to high polarizability of bromine which results in a greater stabilization of the transition state in the case of bromine compared to chlorine. Regardless of the substituent at C5, the positive charge on C4 is greater in the TS compared to the reactant complex for both the Cyt and H₂Cyt. Moreover, as the charges on C4 in the TS increase compared to reactant, ΔG^‡ also increase for the C5 alkyl substituents ( H,  CH₃,  CH₂CH₃,  CH₂CH₂CH₃) in Cyt, while ΔG^‡ decrease in H₂Cyt. In addition, analysis of the frontier MO energies for the transition state structures shows that there is a correlation between the energy of the HOMO–LUMO gap and activation energies.     

The free energy–reaction coordinate profile for α-chymotryptic hydrolysis of a series of N-acetyl-α-L-amino acid methyl esters

The effect of added nucleophiles (methanol and 1,4-butanediol) on the steady-state kinetics of α-chymotryptic hydrolysis of a series of N-acetyl-L-amino acid methyl esters, R-CH(NHCOCH₃)C(O)OCH₃, has been studied. As a result, the rate and equilibrium constants of the ‘elementary’ steps of the enzyme process have been determined. It has also been demonstrated how the free energy–reaction coordinate profile changes if the structure (the size of the hydrocarbon chain) of the ‘chemically inert’ substrate fragment R is varied. The effects observed can be described by the following equation: where ΔG_s and ΔG_a are the free energies of formation of metastable intermediates, i.e., the enzyme–substrate complex and the acylenzyme, respectively, ΔG₂≠ and ΔG₃≠ are the free energies of activation for the chemical steps, i.e., enzyme acylation and acylenzyme hydrolysis, respectively; and ΔG_trans^(R) is the free energy of transfer of substrate group R from water into a nonaqueous solvent. To explain the results obtained, a mechanism for enzyme–substrate interaction is suggested according to which the potential free energy of sorption of substrate group R on the enzyme is 2 ΔG_trans^(R). Such a high gain in the free energy of hydrophobic interaction may only be realized if (a) in the free enzyme the sorption region has a thermodynamically unfavorable contact with the aqueous medium, and (b) water is forced out of the active center as a result of the hydrophobic interaction of substrate group R with the enzyme. Such a model is in agreement with the published x-ray data on the structure of the crystalline enzyme. The kinetic experiment has proved that not all the potential free energy of sorption is realized as binding force. Thus the true free energy of the binding of substrate group R with the protein does not exceed half the maximum value, both in the enzyme–substrate complex and acylenzyme.