Homolytic Bond Dissociation Research Articles

Homolytic dissociation in hydrogen-bonding liquids: energetics of the phenol O?H bond in methanol and the water O?H bond in water

The energetics of the phenol O–H bond in methanol and the water O–H bond in liquid water were investigated by microsolvation modelling and statistical mechanics Monte Carlo simulations. The microsolvation approach was based on density functional theory calculations. Optimised structures for clusters of phenol and the phenoxy radical with one and two methanol molecules are reported. By analysing the differential solvation of phenol and the phenoxy radical in methanol, we predict that the phenol O–H homolytic bond dissociation enthalpy in solution is 24.3±11 kJ/mol above the gas-phase value. The analysis of the water O–H bond dissociation by microsolvation was based on optimised structures of OH•–(H2O)1−6 and –(H2O)1−7 clusters. Microsolvation modelling and statistical mechanics simulations predict that the HO–H bond dissociation enthalpies in the gas phase and in liquid water are very similar. Our results stress the importance of estimating the differences between the solvation enthalpies of the radical species and the parent molecule and the limitations of local models based on microsolvation.

Solvation effects of H2O and DMSO on the O—H bond dissociation energies of substituted phenols

AbstractSolvation effects on the O—H homolytic bond dissociation energies (BDEs) of substituted phenols were studied. It was demonstrated that the BDEs measured in solution in general do not equal the BDEs in the gas phase. Detailed theoretical analyses indicated that a long‐range solvation effect (i.e. the interaction between the solvent and the overall dipole moment of the solute) and a short‐range solvation effect (i.e. the hydrogen bonding between the solute and solvent) were both important for the O—H BDEs in water and in DMSO. Neither one of these two factors by itself could fully explain the experimentally observed solvation effect. However, a combination of these two factors, estimated through a semi‐continuum solvation model, was shown to be reasonably successful in explaining the experimental results. Copyright © 2004 John Wiley & Sons, Ltd.

On the Dissociation of Aromatic Radical Anions in Solution. 1. Formulation and Application to p-Cyanochlorobenzene Radical Anion

A theoretical formulation is presented for the dissociation of aromatic radical anions in solution, [Ar−X]•- → Ar• + X-, and applied to the dissociation of the p-cyanochlorobenzene radical anion [CN−Φ−Cl]•- in several solvents. Key ingredients of the description are (i) the inclusion of the conical intersection (CI) aspects of the problem and (ii) the incorporation of nonequilibrium solvation (within a dielectric continuum solvent description). The CI feature is critical for this cleavage in the ground electronic state, because the required electronic coupling that allows the dissociation vanishes for a planar molecular geometry but is finite for finite C−Cl bending angle. The nonequilibrium solvation aspect is required, because of the inability of the solvent to equilibrate instantly to the changing molecular charge distribution during the radical anion dissociation process. These features are illustrated via the [CN−Φ−Cl]•- dissociation reaction path in a dimethylformamide (DMF) solvent, where C−Cl out-of-plane bending is required to avoid the CI intersection point, which leads to a bent transition state, and where the solvent is shown to reorganize prior to the crossing of the transition state. Reaction rate constants calculated via transition state theory (TST) are in reasonable agreement with experimental values in several solvents. It is also found that intrinsic activation free energies vary linearly with the homolytic bond dissociation energy of the radical anion, which is an experimentally observed feature. Comparison with previous descriptions is given, and inclusion of the CI features of the dissociation is shown to lead to large differences in the reaction activation free energy, which is related to the large electronic coupling, and the energetic cost to bend the C−Cl angle to reach the bent transition state. Possible improvements of the treatment, as well as extensions to other reaction problems, are discussed. Several of the theoretical constructs required for the reaction rate constants and reaction paths implemented in the present paper are developed in the second paper of this series, On the Dissociation of Aromatic Radical Anions in Solution. 2. Reaction Path and Rate Constant Analysis.

First estimation of C4-H bond dissociation energies of NADH and its radical cation in aqueous solution.

The heterolytic and homolytic C4-H bond dissociation energies of NADH and its radical cation (NADH*+) in aqueous solution were estimated according to the reaction of NADH with N,N,N',N'-tetramethyl-p-phenylenediamine radical cation perchlorate (TMPA*+) in aqueous solution. The results show that the values of the heterolytic and homolytic C4-H bond dissociation energies of NADH in aqueous solution are 53.6 and 79.3 kcal/mol, respectively; the values of the heterolytic and homolytic C4-H bond dissociation energies of NADH*+*+ in aqueous solution are 5.1 and 36.3 kcal/mol, respectively, which, to our knowledge, is first reported. This energetic information disclosed in the present work should be believed to furnish hints to the understanding of the mechanisms for the redox interconversions of coenzyme couple NADH/NAD+ in vivo.

Monomeric MnIII/II and FeIII/II complexes with terminal hydroxo and oxo ligands: probing reactivity via O-H bond dissociation energies.

Non-heme manganese and iron complexes with terminal hydroxo or oxo ligands are proposed to mediate the transfer of hydrogen atoms in metalloproteins. To investigate this process in synthetic systems, the monomeric complexes [M(III/II)H(3)1(OH)](-/2-) and [M(III)H(3)1(O)](2-) have been prepared, where M(III/II) = Mn and Fe and [H(3)1](3-) is the tripodal ligand, tris[(N'-tert-butylureaylato)-N-ethyl)]aminato. These complexes have similar primary and secondary coordination spheres, which are enforced by [H(3)1](3-). The homolytic bond dissociation energies (BDEs(O-H)) for the M(III/II)-OH complexes were determined, using experimentally obtained values for the pK(a)(M-OH) and E(1/2) measured in DMSO. This thermodynamic analysis gave BDEs(O-H) of 77(4) kcal/mol for [Mn(II)H(3)1(O-H)](2-) and 66(4) kcal/mol for [Fe(II)H(3)1(O-H)](2-). For the M(III)-OH complexes, [Mn(III)H(3)1(OH)]- and [Fe(III)H(3)1(OH)]-, BDEs(O-H) of 110(4) and 115(4) kcal/mol were obtained. These BDEs(O-H) were verified with reactivity studies with substrates having known X-H bond energies (X = C, N, O). For instance, [Fe(II)H(3)1(OH)](2-) reacts with a TEMPO radical to afford [Fe(III)H(3)1(O)](2-) and TEMPO-H in isolated yields of 60 and 75%, respectively. Consistent with the BDE(O-H) values for [Mn(II)H(3)1(OH)](2-), TEMPO does not react with this complex, yet TEMPO-H (BDE(O-H) = 70 kcal/mol) reacts with [Mn(III)H(3)1(O)](2-), forming TEMPO and [Mn(II)H(3)1(OH)](2-). [Mn(III)H(3)1(O)](2-) and [Fe(III)H(3)1(O)](2-) react with other organic substrates containing C-H bonds less than 80 kcal/mol, including 9,10-dihydroanthracene and 1,4-cyclohexadiene to produce [M(II)H(3)1(OH)](2-) and the appropriate dehydrogenated product in yields of greater than 80%. Treating [Mn(III)H(3)1(O)](2-) and [Fe(III)H(3)1(O)](2-) with phenolic compounds does not yield the product expected from hydrogen atom transfer but rather the protonated complexes, [Mn(III)H(3)1(OH)]- and [Fe(III)H(3)1(OH)]-, which is ascribed to the highly basic nature of the terminal oxo group.

Kinetics of protonation of anthracene radical anions in DMSO by a series of substituted phenols

AbstractThe rate constants kH for proton transfer from a series of substituted phenols to anthracene radical anions formed in DMSO were measured by the voltammetric method. A quadratic Brønsted dependence of RTlnkH against pKa of phenols was observed. The intrinsic activation barrier ΔG0‡ calculated on the basis of the known pKa value for the conjugate acid ArH. of the anthracene radical anion is the same as for the reaction in DMF. The homolytic bond dissociation energy (for ArH.→Ar+H.) was also found to be the same as in DMF. The results obtained are in full agreement with theoretical predictions for protonation of radical anions forming C—H acids, described as the concerted electron and H atom transfer. Copyright © 2003 John Wiley & Sons, Ltd.

Structure‐Activity Relationships for the Toxicity of Substituted Poly‐hydroxylated Benzenes to Tetrahymena pyriformis: Influence of Free Radical Formation

AbstractThe aim of this study was to develop quantitative structure‐activity relationships for the toxicity to Tetrahymena pyriformis of 30 substituted poly‐hydroxylated benzenes. Physico‐chemical descriptors for the expression of free radical formation, associated with the OH moiety on the aromatic ring, were calculated. These included one‐electron equilibrium constants that did and did not account for the oxidation of an OH‐group, homolytic bond dissociation energy (BDE), electronegativity (EN) and absolute hardness (AH), in addition to the distribution coefficient (log D) as a measure of hydrophobicity. The reactivity descriptors were calculated using the semi‐empirical AM1 Hamiltonian in the MOPAC molecular orbital software. Statistically significant two‐parameter QSARs for toxicity were obtained by combination of log D with either BDE or AH. The QSARs suggested that toxicity is associated with hydrophobicity and the probability of radical formation.

Molecular structures, bond energies, and bonding analysis of group 11 cyanides TM(CN) and isocyanides TM(NC) (TM = Cu, Ag, Au).

We report on quantum chemical calculations at the DFT (BP86/TZP) and ab initio (CCSD(T)/III+) levels of the title compounds. The geometries, vibrational spectra, heats of formation, and homolytic and heterolytic bond dissociation energies are given. The calculated bond length of Cu-CN is in reasonable agreement with experiment. The theoretical geometries for CuNC and the other group 11 cyanides and isocyanides which have not been measured as isolated species provide a good estimate for the exact values. The theoretical bond dissociation energies and heats of formation should be accurate with an error limit of +/-5 kcal/mol. The calculation of the vibrational spectra shows that the C-N stretching mode of the cyanides, which lies between 2170 and 2180 cm(-)(1), is IR inactive. The omega(1)(C-N) vibrations of the isocyanides are shifted by approximately 100 cm(-)(1) to lower wavenumbers. They are predicted to have a very large IR intensity. The nature of the metal-ligand interactions was investigated with the help of an energy partitioning analysis in two different ways using the charged fragments TM(+) + CN(-) (TM = transition metal) and the neutral fragments TM(*) + CN(*) as bonding partners. The calculations suggest that covalent interactions are the driving force for the formation of the TM-CN and TM-NC bonds, but the finally formed bonds are better described in terms of interactions between TM(+) and CN(-), which have between 73% and 80% electrostatic character. The contribution of the pi bonding is rather small. The lower energy of the metal cyanides than that of the isocyanides comes from the stronger electrostatic interaction between the more diffuse electron density at the carbon atom of the cyano ligand and the positively charged nucleus of the metal.

Thermochemical and structural studies of Cu(II) and Ni(II) complexes with N, N-diethyl- N′-pivaloylthiourea

The standard ( p 0=0.1 MPa) molar enthalpies of formation of crystalline bis( N, N-diethyl- N′-pivaloylthioureato)copper(II), Cu(PVET) 2, and bis( N, N-diethyl- N′-pivaloylthioureato)nickel(II), Ni(PVET) 2, were measured, at T=298.15 K, by solution–reaction isoperibol calorimetry. The standard molar enthalpies of sublimation, at T=298.15 K, of both complexes were obtained using a Knudsen effusion technique. These values were used to derive the standard molar enthalpy of formation of Cu(PVET) 2 and Ni(PVET) 2 in gaseous phase, and to evaluate the difference between the mean metal–ligand and the hydrogen–ligand bond dissociation enthalpies, in these compounds. The NH homolytic bond dissociation enthalpy in N, N-diethyl- N′-pivaloylthiourea ligand (HPVET) was calculated by high-level density functional theory based calculations. The three-dimensional structures of Cu(PVET) 2 and Ni(PVET) 2 are presented and show a planar coordination around the metal in both molecules.

Remote Substituent Effects on Homolytic Bond Dissociation Energies

In the study we tried to answer two questions. First, does X-Z homolytic bond dissociation energy (BDE) of Y-C6H4-X-Z obey the Hammett relationship? Second, if it does what factors determine the magnitude and sign of the slope (rho+) of Hammett regression against substituent sigma(p)(+) constants? We collected a large number of X-Z BDEs for over one-thousand Y-C6H4-X-Z systems using the RMP2/6-311++G**//UB3LYP/6-31G* method. We found that remote substituent effects on X-Z BDEs are determined by both the ground effect (i.e. stabilization/destabilization of X-Z by the substituents) and the radical effect (i.e. stabilization/destabilization of X. by the substituents). The ground or radical effect is determined by the electron demand of X-Z or X. in the same way as the deprotonation enthalpy of HOOC-C6H4-X-Z or HOOC-C6H4-X. is affected by X-Z or X. . As a result, rho+ (BDE) for X-Z bond homolysis can be quantitatively predicted by using the change in deprotonation enthalpy from HOOC-C6H4-X-Z to HOOC-C6H4-X. .

Transition from hydrogen atom to hydride abstraction by Mn4O4(O2PPh2)6 versus [Mn4O4(O2PPh2)6]+: O-H bond dissociation energies and the formation of Mn4O3(OH)(O2PPh2)6.

Synthesis, characterization, and reactions of the novel manganese-oxo cubane complex [Mn(4)O(4)(O(2)PPh(2))(6)](ClO(4)), 1+ (ClO(4)(-)), are described. Cation 1+ is composed of the [Mn(4)O(4)](7+) core surrounded by six bidentate phosphinate ligands. The proton-coupled electron transfer (pcet) reactions of phenothiazine (pzH), the cation radical (pzH(.+)(ClO(4)(-)), and the neutral pz* radical with 1+ are reported and compared to Mn(4)O(4)(O(2)PPh(2))(6) (1). Compound 1+ (ClO(4)(-)) reacts with excess pzH via four sequential reduction steps that transfer a total of five electrons and four protons to 1+. This reaction forms the doubly dehydrated manganese cluster Mn(4)O(2)(O(2)PPh(2))(6) (2) and two water molecules derived from the corner oxygen atoms. The first pcet step forms the novel complex Mn(4)O(3)(OH)(O(2)PPh(2))(6) (1H) and 1 equiv of the pz+ cation by net hydride transfer from pzH. Spectroscopic characterization of isolated 1H is reported. Reduction of 1 by pzH or a series of para-substituted phenols also produces 1H via net H atom transfer. A lower limit to the homolytic bond dissociation energy (BDE) (1H --> 1 + H) was estimated to be >94 kcal/mol using solution phase BDEs for pzH and para-substituted phenols. The heterolytic BDE was estimated for the hydride transfer reaction 1H --> 1+ + H(-) (BDE approximately 127 kcal/mol). These comparisons reveal the O-H bond in 1H to be among the strongest of any Mn-hydroxo complex measured thus far. In three successive H atom transfer steps, 1H abstracts three hydrogen atoms from three pzH molecules to form complex 2. Complex 2 is shown to be identical to the "pinned butterfly" cluster produced by the reaction of 1 with pzH (Ruettinger, W. F.; Dismukes, G. C. Inorg. Chem. 2000, 39, 1021-1027). The Mn oxidation states in 2 are formally Mn(4)(2II,2III), and no further reduction occurs in excess pzH. By contrast, outer-sphere electron-only reductants such as cobaltacene reduce both 1+ and 1 to the all Mn(II) oxidation level and cause cluster fragmentation. The reaction of pzH(.+) with 1+ produces 1H and the pz+ cation by net hydrogen atom transfer, and terminates at 1 equiv of pzH(.+) with no further reaction at excess. By contrast, pz* does not react with 1+ at all, indicating that reduction of 1+ by electron transfer to form pz+ does not occur without a proton (pcet to 1+ is thermodynamically required). Experimental free energy changes are shown to account for these pcet reactions and the absence of electron transfer for any of the phenothiazine series. Hydrogen atom abstraction from substrates by 1 versus hydride abstraction by 1(+ )()illustrates the transition to two-electron one-proton pcet chemistry in the [Mn(4)O(4)](7+) core that is understood on the basis of free energy consideration. This transition provides a concrete example of the predicted lowest-energy pathway for the oxidation of two water molecules to H(2)O(2) as an intermediate within the photosynthetic water-oxidizing enzyme (vs sequential one-electron/proton steps). The implications for the mechanism of photosynthetic water splitting are discussed.

Pauling's electronegativity equation and a new corollary accurately predict bond dissociation enthalpies and enhance current understanding of the nature of the chemical bond.

Contrary to other recent reports, Pauling's original electronegativity equation, applied as Pauling specified, describes quite accurately homolytic bond dissociation enthalpies of common covalent bonds, including highly polar ones, with an average deviation of +/-1.5 kcal mol(-1) from literature values for 117 such bonds. Dissociation enthalpies are presented for more than 250 bonds, including 79 for which experimental values are not available. Some previous evaluations of accuracy gave misleadingly poor results by applying the equation to cases for which it was not derived and for which it should not reproduce experimental values. Properly interpreted, the results of the equation provide new and quantitative insights into many facets of chemistry such as radical stabilities, factors influencing reactivity in electrophilic aromatic substitutions, the magnitude of steric effects, conjugative stabilization in unsaturated systems, rotational barriers, molecular and electronic structure, and aspects of autoxidation. A new corollary of the original equation expands its applicability and provides a rationale for previously observed empirical correlations. The equation raises doubts about a new bonding theory. Hydrogen is unique in that its electronegativity is not constant.

Quantitative structure toxicity relationships for phenols in isolated rat hepatocytes

Quantitative structure toxicity relationship (QSTR) equations were obtained to predict and describe the cytotoxicity of 31 phenols using log LD 50 as a concentration to induce 50% cytotoxicity of isolated rat hepatocytes in 2 h and log P as octanol/water partitioning: log LD 50 (μM)=−0.588(±0.059)log P+4.652(±0.153) ( n=27, r 2=0.801, s=0.261, P<1×10 −9). Hydroquinone, catechol, 4-nitrophenol, and 2,4-dinitrophenol were outliers for this equation. When the ionization constant p K a was considered as a contributing factor a two-parameter QSTR equation was derived: log LD 50 (μM)=−0.595(±0.051)log P+0.197(±0.029)p K a+2.665(±0.281) ( n=28, r 2=0.859, s=0.218, P<1×10 −6). Using σ +, the Brown variation of the Hammet electronic constant, as a contributing parameter, the cytotoxicity of phenols towards hepatocytes were defined by log LD 50 (μM)=−0.594(±0.052)log P−0.552(±0.085) σ ++4.540(±0.132) ( n=28, r 2=0.853, s=0.223, P<1×10 −6). Replacing σ + with the homolytic bond dissociation energy (BDE) for (X-PhOH+PhO →X-PhO +PhOH) led to log LD 50 (μM)=−0.601(±0.066)log P−0.040(±0.018)BDE+4.611(±0.166) ( n=23, r 2=0.827, s=0.223, P<0.05). Hydroquinone, catechol and 2-nitrophenol were outliers for the above equations. Using redox potential and log P led to a new correlation: log LD 50 (μM)=−0.529(±0.135)log P+2.077(±0.892) E p/2+2.806(±0.592) ( n=15, r 2=0.561, s=0.383, P<0.05) with 4-nitrophenol as an outlier. Our findings indicate that phenols with higher lipophilicity, BDE, or σ + values or with lower p K a and redox potential were more toxic towards hepatocytes. We also showed that a collapse of hepatocyte mitochondrial membrane potential preceded the cytotoxicity of most phenols. Our study indicates that one or a combination of mechanisms; i.e. mitochondrial uncoupling, phenoxy radicals, or phenol metabolism to quinone methides and quinones, contribute to phenol cytotoxicity towards hepatocytes depending on the phenol chemical structure.

Concerted rearrangement versus heterolytic cleavage in anionic [2,3]- and [3,3]-sigmatropic shifts. A DFT study of relationships among anion stabilities, mechanisms, and rates.

The anionic [2,3] sigmatropic Wittig rearrangements of deprotonated 4-hetera-1-pentenes and the anionic [3,3] sigmatropic Cope rearrangements of 3-substituted-1,5-hexadienes were explored by using density functional theory calculations. While the deprotonated anionic 3-hydroxy-1,5 hexadiene (2a), 3-thiohydroxy-1,5-hexadiene (2c), and 3-formamidyl-1,5-hexadiene (2d) Cope substrates undergo concerted rearrangements, the deprotonated anionic 3-amino-1,5-hexadiene (2b) and 3-methyl-1,5-hexadiene (2e) Cope substrates follow nonconcerted cleavage/recombination pathways. We have also found that the gas-phase Wittig (1a), aza-Wittig (1b), and carba-Wittig (1c) reactions proceed via nonconcerted cleavage/recombination pathways. These results are compared with previous results on the Cope rearrangements of deprotonated anionic 3-hydroxy-1,5-hexadiene and 3-amino-1,5-hexadiene anions. A previously established model that heterolytic and homolytic bond dissociation energies can be used to predict how anionic amino- and oxy-Cope substrates will react is generalized to account for the reactivity of other Cope substrates as well as for the Wittig rearrangements. There is also a relationship between the basicity of the anionic substituent in the Cope rearrangement and the reaction pathway: the more basic the substituent anion, the less stable it is, and the more likely it is that cleavage will occur. A first step toward studying these reactions in solution was also taken by calculating energetics for some of the rearrangements with a lithium counterion present.

Determination of the C4-H bond dissociation energies of NADH models and their radical cations in acetonitrile.

Heterolytic and homolytic bond dissociation energies of the C4-H bonds in ten NADH models (seven 1,4-dihydronicotinamide derivatives, two Hantzsch 1,4-dihydropyridine derivatives, and 9,10-dihydroacridine) and their radical cations in acetonitrile were evaluated by titration calorimetry and electrochemistry, according to the four thermodynamic cycles constructed from the reactions of the NADH models with N,N,N',N'-tetramethyl-p-phenylenediamine radical cation perchlorate in acetonitrile (note: C9-H bond rather than C4-H bond for 9,10-dihydroacridine; however, unless specified, the C9-H bond will be described as a C4-H bond for convenience). The results show that the energetic scales of the heterolytic and homolytic bond dissociation energies of the C4-H bonds cover ranges of 64.2-81.1 and 67.9-73.7 kcal mol(-1) for the neutral NADH models, respectively, and the energetic scales of the heterolytic and homolytic bond dissociation energies of the (C4-H)(.+) bonds cover ranges of 4.1-9.7 and 31.4-43.5 kcal mol(-1) for the radical cations of the NADH models, respectively. Detailed comparison of the two sets of C4-H bond dissociation energies in 1-benzyl-1,4-dihydronicotinamide (BNAH), Hantzsch 1,4-dihydropyridine (HEH), and 9,10-dihydroacridine (AcrH(2)) (as the three most typical NADH models) shows that for BNAH and AcrH(2), the heterolytic C4-H bond dissociation energies are smaller (by 3.62 kcal mol(-1)) and larger (by 7.4 kcal mol(-1)), respectively, than the corresponding homolytic C4-H bond dissociation energy. However, for HEH, the heterolytic C4-H bond dissociation energy (69.3 kcal mol(-1)) is very close to the corresponding homolytic C4-H bond dissociation energy (69.4 kcal mol(-1)). These results suggests that the hydride is released more easily than the corresponding hydrogen atom from BNAH and vice versa for AcrH(2), and that there are two almost equal possibilities for the hydride and the hydrogen atom transfers from HEH. Examination of the two sets of the (C4-H)(.+) bond dissociation energies shows that the homolytic (C4-H)(.+) bond dissociation energies are much larger than the corresponding heterolytic (C4-H)(.+) bond dissociation energies for the ten NADH models by 23.3-34.4 kcal mol(-1); this suggests that if the hydride transfer from the NADH models is initiated by a one-electron transfer, the proton transfer should be more likely to take place than the corresponding hydrogen atom transfer in the second step. In addition, some elusive structural information about the reaction intermediates of the NADH models was obtained by using Hammett-type linear free-energy analysis.

Thiyl Radicals Abstract Hydrogen Atoms from the αC−H Bonds in Model Peptides: Absolute Rate Constants and Effect of Amino Acid Structure

Thiyl radicals are important intermediates in biological oxidative stress and enzymatic reactions, for example, the ribonucleotide reductases. On the basis of the homolytic bond dissociation energies (BDEs) only, the (alpha)C-H bonds of peptides and proteins would present suitable targets for hydrogen abstraction by thiyl radicals. However, additional parameters such as polar and conformational effects may control such hydrogen-transfer processes. To evaluate the potential of thiyl radicals for hydrogen abstraction from (alpha)C-H bonds, we provide the first absolute rate constants for these reactions with model peptides. Thiyl radicals react with (alpha)C-H bonds with rate constants between 1.7 x 10(3) M(-1) s(-1) (N-acetylproline amide) and 4 x 10(5) M(-1) s(-1) (sarcosine anhydride). However, the correlation of rate constants with BDEs is poor. Rather, these reactions may be controlled by conformation and dynamic flexibility around the (alpha)C-H bonds.

Gas-Phase Thermodynamic Properties of Dichlorophenols Determined from Density Functional Theory Calculations

Density functional theory has been used to investigate gas-phase thermodynamic properties of phenol and dichlorophenols. Molecular geometries, energies, and vibrational frequencies were computed at the B3LYP and BP86 levels of theory. At T = 298.15 K, calculated standard enthalpies of formation are in excellent agreement with experimental data. The average deviation between calculated and experimental values is of about 2.3 kJ/mol, and in some cases, theoretical values fall within experimental uncertainty. Other properties for which only a few experimental results were available in the literature were also calculated, namely, O−H homolytic bond dissociation energies, gas-phase acidities, ionization energies, and proton and electron affinities.

Homolytic bond dissociation energies associated with acyl radicals and electron demands of acyl groupsElectronic supplementary information (ESI) available: Effects of method and basis on geometry optimizations, radical structures, bond orders, spins and bond lengths. See http://www.rsc.org/suppdata/cp/b2/b211078d/

Composite ab initio G3 and CBS-4M methods were used to calculate the homolytic bond dissociation energies (BDE) associated with various acyl radicals (R–C(˙)O). The structures and the vibration properties of the related acyl compounds and radicals were also obtained and discussed. It was found that the BDEs and the structures of the acyl compounds are affected by the electron demand (i.e. electron withdrawing or donating ability) of the acyl groups. According to the Hammett analysis, the electron withdrawing ability of the acyl groups and radicals decreases in the order CO–CN > CO–Cl > CO–F > C(˙)O > CO–H > CO–OH > CO–SCH3 > CO–CH3 > CO–NH2. This order is not consistent with the electronegativity of each group. Therefore, it is the electron demand, not the electronegativity, that determines the substituent effects on the BDEs associated with the acyl radicals.

Ni(Et2PCH2NMeCH2PEt2)2]2+ as a functional model for hydrogenases.

The reaction of Et(2)PCH(2)N(Me)CH(2)PEt(2) (PNP) with [Ni(CH(3)CN)(6)](BF(4))(2) results in the formation of [Ni(PNP)(2)](BF(4))(2), which possesses both hydride- and proton-acceptor sites. This complex is an electrocatalyst for the oxidation of hydrogen to protons, and stoichiometric reaction with hydrogen forms [HNi(PNP)(PNHP)](BF(4))(2), in which a hydride ligand is bound to Ni and a proton is bound to a pendant N atom of one PNP ligand. The free energy associated with this reaction has been calculated to be -5 kcal/mol using a thermodynamic cycle. The hydride ligand and the NH proton undergo rapid intramolecular exchange with each other and intermolecular exchange with protons in solution. [HNi(PNP)(PNHP)](BF(4))(2) undergoes reversible deprotonation to form [HNi(PNP)(2)](BF(4)) in acetonitrile solutions (pK(a) = 10.6). A convenient synthetic route to the PF(6)(-) salt of this hydride involves the reaction of PNP with Ni(COD)(2) to form Ni(PNP)(2), followed by protonation with NH(4)PF(6). A pK(a) of value of 22.2 was measured for this hydride. This value, together with the half-wave potentials of [Ni(PNP)(2)](BF(4))(2), was used to calculate homolytic and heterolytic Ni-H bond dissociation free energies of 55 and 66 kcal/mol, respectively, for [HNi(PNP)(2)](PF(6)). Oxidation of [HNi(PNP)(2)](PF(6)) has been studied by cyclic voltammetry, and the results are consistent with a rapid migration of the proton from the Ni atom of the resulting [HNi(PNP)(2)](2+) cation to the N atom to form [Ni(PNP)(PNHP)](2+). Estimates of the pK(a) values of the NiH and NH protons of these two isomers indicate that proton migration from Ni to N should be favorable by 1-2 pK(a) units. Cyclic voltammetry and proton exchange studies of [HNi(depp)(2)](PF(6)) (where depp is Et(2)PCH(2)CH(2)CH(2)PEt(2)) are also presented as control experiments that support the important role of the bridging N atom of the PNP ligand in the proton exchange reactions observed for the various Ni complexes containing the PNP ligand. Similarly, structural studies of [Ni(PNBuP)(2)](BF(4))(2) and [Ni(PNP)(dmpm)](BF(4))(2) (where PNBuP is Et(2)PCH(2)N(Bu)CH(2)PEt(2) and dmpm is Me(2)PCH(2)PMe(2)) illustrate the importance of tetrahedral distortions about Ni in determining the hydride acceptor ability of Ni(II) complexes.

Equilibrium acidities and homolytic bond dissociation energies of acidic C-H bonds in alpha-arylacetophenones and related compounds.

The equilibrium acidities (pK(AH)s) and the oxidation potentials of the congugate anions [E(ox)(A(-))s] were determined in dimethyl sulfoxide (DMSO) for eight ketones of the structure GCOCH(3) and 20 of the structure RCOCH(2)G, (where R = alkyl, phenyl and G = alkyl, aryl). The homolytic bond dissociation energies (BDEs) for the acidic C-H bonds of the ketones were estimated using the equation BDE(AH) = 1.37pK(AH) + 23.1E(ox)(A(-)) + 73.3. While the equilibrium acidities of GCOCH(3) were found to be dependent on the remote substituent G, the BDE values for the C-H bonds remained essentially invariant (93.5 +/- 0.5 kcal/mol). A linear correlation between pK(AH) values and [E(ox)(A(-))s] was found for the ketones. For RCOCH(2)G ketones, both pK(AH) and BDE values for the adjacent C-H bonds are sensitive to the nature of the substituent G. However, the steric bulk of the aryl group tends to exert a leveling effect on BDEs. The BDE of alpha-9-anthracenylacetophenone is higher than that of alpha-2-anthracenylacetophenone by 3 kcal/mol, reflecting significant steric inhibition of resonance in the 9-substituted system. A range of 80.7-84.4 kcal/mol is observed for RCOCH(2)G ketones. The results are discussed in terms of solvation, steric, and resonance effects. Ab initio density functional theory (DFT) calculations are employed to illustrate the effect of steric interactions on radical and anion geometries. The DFT results parallel the trends in the experimental BDEs of alpha-arylacetophenones.