Enthalpies of hydrogen-bonds in alpha-helical peptides. An ONIOM DFT/AM1 study

We report the enthalpy differences between alpha-helical and extended beta-strand conformations of acetyl(Ala)nNH2, for n = 8, 10, 12-17, calculated using molecular (MO) orbital theory from complete vibrational analyses of the optimized species. The calculations used the ONIOM method with B3LYP/D95(d.p) as the high and AM1 as the low levels. The incremental change in enthalpy upon addition of one Ala to a growing beta-strand defined using the hypothetical polycondensation reaction, n Ala + CH3COOH + NH3 --> acetyl(Ala)nNH2 + n H2O, reaches its asymptotic limit of -1.4 kcal/mol at n = 10, while that for the alpha-helix continues to increase in magnitude at n = 17. The asymptotic limit of the enthalpic preference of the alpha-helix over beta-strand is estimated to be about 3 kcal/mol, while that for n = 17 is 11.99 kcal/mol or about 0.8 kcal/mol/H-bond, which is similar to measured values for polyalanines of this size in aqueous solution.     

Theoretical study of transition state structure and reaction enthalpy of the F + H2-->HF + H reaction by a diffusion quantum Monte Carlo approach

Ab initio calculations of transition state structure and reaction enthalpy of the F + H2-->HF + H reaction has been carried out by the fixed-node diffusion quantum Monte Carlo method in this study. The Monte Carlo sampling is based on the Ornstein-Uhlenbeck random walks guided by a trial wave function constructed from the floating spherical Gaussian orbitals and spherical Gaussian geminals. The Monte Carlo calculated barrier height of 1.09(16) kcal/mol is consistent with the experimental values, 0.86(10)/1.18(10) kcal/mol, and the calculated value from the multireference-type coupled-cluster (MRCC) calculation with the aug-cc-pVQZ(F)/cc-pVQZ(H) basis set, 1.11 kcal/mol. The Monte Carlo-based calculation also gives a similar value of the reaction enthalpy, -32.00(4) kcal/mol, compared with the experimental value, -32.06(17) kcal/mol, and the calculated value from a MRCC/aug-cc-pVQZ(F)/cc-pVQZ(H) calculation, -31.94 kcal/mol. This study clearly indicates a further application of the random-walk-based approach in the field of quantum chemical calculation.     

On the mechanism of (PCP)Ir-catalyzed acceptorless dehydrogenation of alkanes: a combined computational and experimental study

Pincer complexes of the type ((R)PCP)IrH(2), where ((R)PCP)Ir is [eta(3)-2,6-(R(2)PCH(2))(2)C(6)H(3)]Ir, are the most effective catalysts reported to date for the "acceptorless" dehydrogenation of alkanes to yield alkenes and free H(2). We calculate (DFT/B3LYP) that associative (A) reactions of ((Me)PCP)IrH(2) with model linear (propane, n-PrH) and cyclic (cyclohexane, CyH) alkanes may proceed via classical Ir(V) and nonclassical Ir(III)(eta(2)-H(2)) intermediates. A dissociative (D) pathway proceeds via initial loss of H(2), followed by C-H addition to ((Me)PCP)Ir. Although a slightly higher energy barrier (DeltaE(+ +)) is computed for the D pathway, the calculated free-energy barrier (DeltaG(+ +)) for the D pathway is significantly lower than that of the A pathway. Under standard thermodynamic conditions (STP), C-H addition via the D pathway has DeltaG(o)(+ +) = 36.3 kcal/mol for CyH (35.1 kcal/mol for n-PrH). However, acceptorless dehydrogenation of alkanes is thermodynamically impossible at STP. At conditions under which acceptorless dehydrogenation is thermodynamically possible (for example, T = 150 degrees C and P(H)2 = 1.0 x 10(-7) atm), DeltaG(+ +) for C-H addition to ((Me)PCP)Ir (plus a molecule of free H(2)) is very low (17.5 kcal/mol for CyH, 16.7 kcal/mol for n-PrH). Under these conditions, the rate-determining step for the D pathway is the loss of H(2) from ((Me)PCP)IrH(2) with DeltaG(D)(+ +) approximately DeltaH(D)(+ +) = 27.2 kcal/mol. For CyH, the calculated DeltaG(o)(+ +) for C-H addition to ((Me)PCP)IrH(2) on the A pathway is 35.2 kcal/mol (32.7 kcal/mol for n-PrH). At catalytic conditions, the calculated free energies of C-H addition are 31.3 and 33.7 kcal/mol for CyH and n-PrH addition, respectively. Elimination of H(2) from the resulting "seven-coordinate" Ir-species must proceed with an activation enthalpy at least as large as the enthalpy change of the elimination step itself (DeltaH approximately 11-13 kcal/mol), and with a small entropy of activation. The free energy of activation for H(2) elimination (DeltaG(A)(+ +)) is hence found to be greater than ca. 36 kcal/mol for both CyH and n-PrH under catalytic conditions. The overall free-energy barrier of the A pathway is calculated to be higher than that of the D pathway by ca. 9 kcal/mol. Reversible C-H(D) addition to ((R)PCP)IrH(2) is predicted to lead to H/D exchange, because the barriers for hydride scrambling are extremely low in the "seven-coordinate" polyhydrides. In agreement with calculation, H/D exchange is observed experimentally for several deuteriohydrocarbons with the following order of rates: C(6)D(6) > mesitylene-d(12) > n-decane-d(22) > cyclohexane-d(12). Because H/D exchange in cyclohexane-d(12) solution is not observed even after 1 week at 180 degrees C, we estimate that the experimental barrier to cyclohexane C-D addition is greater than 36.4 kcal/mol. This value is considerably greater than the experimental barrier for the full catalytic dehydrogenation cycle for cycloalkanes (ca. 31 kcal/mol). Thus, the experimental evidence, in agreement with calculation, strongly indicates that the A pathway is not kinetically viable as a segment of the "acceptorless" dehydrogenation cycle.     

2-Pyridinethiol/2-pyridinethione tautomeric equilibrium. A comparative experimental and computational study

The gas phase and solvent dependent preference of the tautomerization between 2-pyridinethiol (2SH) and 2-pyridinethione (2S) has been assessed using variable temperature Fourier transform infrared (FTIR) experiments, as well as ab initio and density functional theory computations. No spectroscopic evidence (nu(S)(-)(H) stretch) for 2SH was observed in toluene, C(6)D(6), heptane, or methylene chloride solutions. Although, C(s)() 2SH is 2.61 kcal/mol more stable than C(s)() 2S (CCSD(T)/cc-pVTZ//B3LYP/6-311+G(3df,2p)+ZPE), cyclohexane solvent-field relative energies (IPCM-MP2/6-311+G(3df,2p)) favor 2S by 1.96 kcal/mol. This is in accord with the FTIR observations and in quantitative agreement with the -2.6 kcal/mol solution (toluene or C(6)D(6)) calorimetric enthalpy for the 2S/2SH tautomerization favoring the thione. As the intramolecular transition state for the 2S, 2SH tautomerization (2TS) lies 25 (CBS-Q) to 30 kcal/mol (CCSD/cc-pVTZ) higher in energy than either tautomer, tautomerization probably occurs in the hydrogen bonded dimer. The B3LYP/6-311+G(3df,2p) optimized C(2) 2SH dimer is 10.23 kcal/mol + ZPE higher in energy than the C(2)(h)() 2S dimer and is only 2.95 kcal/mol + ZPE lower in energy than the C(2) 2TS dimer transition state. Dimerization equilibrium measurements (FTIR, C(6)D(6)) over the temperature range 22-63 degrees C agree: K(eq)(298) = 165 +/- 40 M(-)(1), DeltaH = -7.0 +/- 0.7 kcal/mol, and DeltaS = -13.4 +/- 3.0 cal/(mol deg). The difference between experimental and B3LYP/6-311+G(3df,2p) [-34.62 cal/(mol deg)] entropy changes is due to solvent effects. The B3LYP/6-311+G(3df,2p) nucleus independent chemical shifts (NICS) are -8.8 and -3.5 ppm 1 A above the 2SH and 2S ring centers, respectively, and the thiol is aromatic. Although the thione is not aromatic, it is stabilized by the thioamide resonance. In solvent, the large 2S dipole, 2-3 times greater than 2SH, favors the thione tautomer and, in conclusion, 2S is thermodynamically more stable than 2SH in solution.     

Dicyclobuta[de,ij]naphthalene and dicyclopenta[cd,gh]pentalene: a theoretical study

The structures, energetics, and aromatic character of dicyclobuta[de,ij]naphthalene, 1, dicyclopenta[cd,gh]pentalene, 2, dihydrodicyclobuta[de,ij]naphthalene, 3, and dihydrocyclopenta[cd,gh]pentalene, 4, have been examined at the B3LYP/6-311++G//B3LYP/6-31G level of theory. All molecules are bowl-shaped, and the pentalene isomers, 2 and 4, are most stable. A comparison with other C(12)H(6) and C(12)H(8) isomers indicates that 2 is approximately 25 kcal/mol less stable than 1,5,9-tridehydro[12]annulene and 4 is approximately 100 kcal/mol higher in energy than acenaphthylene, both of which are synthetically accessible. The transition state structure for bowl-to-bowl inversion of 1 is planar (D(2)(h)()) and lies 30.9 kcal/mol higher in energy than the ground state; the transition state for inversion of 2 is C(2)(h)() and lies 46.6 kcal/mol higher in energy. Symmetry considerations, bond length alternations, and NICS values (a magnetic criterion) all indicate that the ground states of 1, 3, and 4 are very aromatic; however, HOMA values (a measure of bond delocalization) indicate that 3S and 4S are aromatic but that 1S is less so. NICS values for the ground state of 2 strongly indicate aromaticity; however, bond localization, symmetry, and HOMA values argue otherwise.     

Reaction mechanism of naphthyl radicals with molecular oxygen. 1. Theoretical study of the potential energy surface

Potential energy surfaces (PESs) of the reactions of 1- and 2-naphthyl radicals with molecular oxygen have been investigated at the G3(MP2,CC)//B3LYP/6-311G** level of theory. Both reactions are shown to be initiated by barrierless addition of O(2) to the respective radical sites of C(10)H(7). The end-on O(2) addition leading to 1- and 2-naphthylperoxy radicals exothermic by 45-46 kcal/mol is found to be more preferable thermodynamically than the side-on addition. At the subsequent reaction step, the chemically activated 1- and 2-C(10)H(7)OO adducts can eliminate an oxygen atom leading to the formation of 1- and 2-naphthoxy radical products, respectively, which in turn can undergo unimolecular decomposition producing indenyl radical + CO via the barriers of 57.8 and 48.3 kcal/mol and with total reaction endothermicities of 14.5 and 10.2 kcal/mol, respectively. Alternatively, the initial reaction adducts can feature an oxygen atom insertion into the attacked C(6) ring leading to bicyclic intermediates a10 and a10' (from 1-naphthyl + O(2)) or b10 and b10' (from 2-naphthyl + O(2)) composed from two fused six-member C(6) and seven-member C(6)O rings. Next, a10 and a10' are predicted to decompose to C(9)H(7) (indenyl) + CO(2), 1,2-C(10)H(6)O(2) (1,2-naphthoquinone) + H, and 1-C(9)H(7)O (1-benzopyranyl) + CO, whereas b10 and b10' would dissociate to C(9)H(7) (indenyl) + CO(2), 2-C(9)H(7)O (2-benzopyranyl) + CO, and 1,2-C(10)H(6)O(2) (1,2-naphthoquinone) + H. On the basis of this, the 1-naphthyl + O(2) reaction is concluded to form the following products (with the overall reaction energies given in parentheses): 1-naphthoxy + O (-15.5 kcal/mol), indenyl + CO(2) (-123.9 kcal/mol), 1-benzopyranyl + CO (-97.2 kcal/mol), and 1,2-naphthoquinone + H (-63.5 kcal/mol). The 2-naphthyl + O(2) reaction is predicted to produce 2-naphthoxy + O (-10.9 kcal/mol), indenyl + CO(2) (-123.7 kcal/mol), 2-benzopyranyl + CO (-90.7 kcal/mol), and 1,2-naphthoquinone + H (-63.2 kcal/mol). Simplified kinetic calculations using transition-state theory computed rate constants at the high-pressure limit indicate that the C(10)H(7)O + O product channels are favored at high temperatures, while the irreversible oxygen atom insertion first leading to the a10 and a10' or b10 and b10' intermediates and then to their various decomposition products is preferable at lower temperatures. Among the decomposition products, indenyl + CO(2) are always most favorable at lower temperatures, but the others, 1,2-C(10)H(6)O(2) (1,2-naphthoquinone) + H (from a10 and b10'), 1-C(9)H(7)O (1-benzopyranyl) + CO (from a10'), and 2-C(10)H(7)O (2-benzopyranyl) + O (from b10 and minor from b10'), may notably contribute or even become major products at higher temperatures.     

Carboranes and baskets from reaction of B4H10 with allene

The reaction of the boron hydride B4H10 with allene was studied at the CCSD(T)/6-311+G(d)//MP2/6-31G(d) level. The mechanism is surprisingly complex with 44 transition states and several branching points located. The four carboranes and one basket that have been observed experimentally are all connected by pathways that have very similar free energies of activation. In addition, two new structures, a basket (2,4-(CH2CH2CH2)B4H8, 5a) and a "classical" structure (1,4-(Me2C)bisdiborane, 7), which might be obtained from the B4H10 + C3H4 reaction under the right conditions (hot/cold, quenched, etc.) have been identified. The first branch point in the reaction is the competition between H2 elimination from B4H10 (DeltaG(298 K) = 32.2 kcal/mol) and the hydroboration of allene by B4H10 (DeltaG(298 K) = 31.3 kcal/mol). The next branch point in the hydroboration mechanism controls the formation of 2,4-(MeCHCH2)B4H8 (1) (DeltaG(298 K) = 31.5 kcal/mol) and arachno-1,2/arachno-1,3-Me2-1-CB4H7 (8 and 8a) (DeltaG(298 K) = 34.3 kcal/mol). Another branch point in the H2-elimination mechanism controls the formation of 1-Me-2,5-micro-CH2-1-CB4H7 (29) (DeltaG(298 K) = 0.1 kcal/mol) and 2,5-micro-CHMe-1-CB4H7 (25/26) (DeltaG(298 K) = 7.3 kcal/mol). Formation of 2-Me-2,3-C2B4H7, a carborane observed in the reaction of methylacetylene with B4H10, is calculated to be blocked by a high barrier for H2 elimination. All free energies are relative to B4H10 + allene. An interesting reaction step discovered is the "reverse hydroboration step" in which a hydrogen atom is transferred from carbon back to boron, which allows a CH hydrogen to shuttle between the terminal and central carbon of allene.     

Electronic structure of 1,3,5-triaminobenzene trication and related triradicals: doublet versus quartet ground state

Quantum chemical calculations have been carried out to determine the electronic ground state of the parent 1,3,5-triaminobenzene trication triradical (TAB3+,C6H9N3 3+) containing a six-membered benzene ring coupled with three exocyclic amino NH(*+)2 groups, each containing an unpaired electron, as the simplest model for high-spin polyarylamine polycations. Related triradicals, including the 1,3,5-trimethylenebenzene (TMB, C9H9) and its nitrogen derivatives such as the monocation C8H9N+, the dication C7H9N2 2+, and the neutral C8H8N, C7H7N2, and C6H6N3 systems containing NH groups, have also been considered. Results obtained using the CASSCF [multiconfigurational complete active space (SCF--self-consistent field)] method, with active spaces ranging from (9e/9o) to (15e/12o), followed by second-order perturbation theory [CASPT2 and MS-CASPT2 (MS--multistate)] with polarized 6-311G(d,p) and natural orbital (ANO-L) basis sets reveal the following: (i) both TAB3+ and TMB (D3h) have a quartet 4A"1 ground state with doublet-quartet 2B1-4A"1 energy gaps of 8.0+/-2.0 and 12.4+/-2.0 kcal/mol, respectively; (ii) in the neutral N series, the quartet state remains the electronic ground state, irrespective of the number of N atoms, but each with slightly reduced gap, 11 kcal/mol for C8H8N (4A"), 10 kcal/mol for C7H7N2 (4A2), and 9 kcal/mol for C6H6N3 (4A2); and (iii) the ground state of monoamino cation and diamino dication is a low-spin doublet state (2B1 for C8H9N+ and 2A2 for C7H9N2 2+) and lying well below the corresponding quartet state by 10 and 12 kcal/mol, respectively. In the monocationic and dicationic amino systems, a slight preference is found for the low-spin state, apparently violating Hund's rule. This effect is due to the splitting of the orbital energies and the presence of the positive charge whose delocalization strongly modifies the electronic distribution and some structural features. In the latter cations, the positive charge basically pushes unpaired electrons onto the ring forming a kind of distonic radical cations and thus gives a preference for a low-spin state.     

Reaction of phenyl radicals with acetylene: quantum chemical investigation of the mechanism and master equation analysis of the kinetics

The mechanism of the C(6)H(5) + C(2)H(2) reaction has been investigated by various quantum chemical methods. Electrophilic addition to the CC triple bond is found to be the only important mode of phenyl radical attack on acetylene. The initially formed chemically activated C(6)H(5)C(2)H(2) adducts may follow several isomerization pathways in competition with collisional stabilization and H-elimination. Thermochemistry of various decomposition and isomerization channels is evaluated by the G2M method. For key intermediates, the following standard enthalpies of formation have been deduced from isodesmic reactions: 94.2 +/- 2.0 kcal/mol (C(6)H(5)CHCH), 86.4 +/- 2.0 kcal/mol (C(6)H(5)CCH(2)), and 95.5 +/- 1.8 kcal/ mol (o-C(6)H(4)C(2)H(3)). The accuracy of theoretical predictions was examined through extensive comparisons with available experimental and theoretical data. The kinetics and product branching of the C(6)H(5) + C(2)H(2) reaction have been evaluated by weak collision master equation/Rice-Ramsperger-Kassel-Marcus (RRKM) analysis of the truncated kinetic model including only kinetically important transformations of the isomeric C(8)H(7) radicals. Available experimental kinetic data can be quantitatively reproduced by calculation with a minor adjustment of the C(6)H(5) addition barrier from 3.7 to 4.1 kcal/mol. Our predicted total rate constant, k(R1) = (1.29 x 10(10))T(0.834) exp(-2320/T) cm(3) mol(-)(1) s(-)(1), is weakly dependent on P and corresponds to the phenylation process under combustion conditions (T > 1000 K).     

Active Thermochemical Tables: accurate enthalpy of formation of hydroperoxyl radical, HO2

Through the use of the Active Thermochemical Tables approach, the best currently available enthalpy of formation of HO2 has been obtained as delta(f)H(o)298 (HO2) = 2.94 +/- 0.06 kcal mol(-1) (3.64 +/- 0.06 kcal mol(-1) at 0 K). The related enthalpy of formation of the positive ion, HO2+, within the stationary electron convention is delta(f)H(o)298 (HO2+) = 264.71 +/- 0.14 kcal mol(-1) (265.41 +/- 0.14 kcal mol(-1) at 0 K), while that for the negative ion, HO2- (within the same convention), is delta(f)H(o)298 (HO2-) = -21.86 +/- 0.11 kcal mol(-1) (-21.22 +/- 0.11 kcal mol(-1) at 0 K). The related proton affinity of molecular oxygen is PA298(O2) = 100.98 +/- 0.14 kcal mol(-1) (99.81 +/- 0.14 kcal mol(-1) at 0 K), while the gas-phase acidity of H2O2 is delta(acid)G(o)298 (H2O2) = 369.08 +/- 0.11 kcal mol(-1), with the corresponding enthalpy of deprotonation of H2O2 of delta(acid)H(o)298 (H2O2) = 376.27 +/- 0.11 kcal mol(-1) (375.02 +/- 0.11 kcal mol(-1) at 0 K). In addition, a further improved enthalpy of formation of OH is briefly outlined, delta(f)H(o)298 (OH) = 8.93 +/- 0.03 kcal mol(-1) (8.87 +/- 0.03 kcal mol(-1) at 0 K), together with new and more accurate enthalpies of formation of NO, delta(f)H(o)298 (NO) = 21.76 +/- 0.02 kcal mol(-1) (21.64 +/- 0.02 kcal mol(-1) at 0 K) and NO2, delta(f)H(o)298 (NO2) = 8.12 +/- 0.02 kcal mol(-1) (8.79 +/- 0.02 kcal mol(-1) at 0 K), as well as H(2)O(2) in the gas phase, delta(f)H(o)298 (H2O2) = -32.45 +/- 0.04 kcal mol(-1) (-31.01 +/- 0.04 kcal mol(-1) at 0 K). The new thermochemistry of HO2, together with other arguments given in the present work, suggests that the previous equilibrium constant for NO + HO2 --> OH + NO2 was underestimated by a factor of approximately 2, implicating that the OH + NO2 rate was overestimated by the same factor. This point is experimentally explored in the companion paper of Srinivasan et al. (next paper in this issue).     

Reaction mechanism between carbonyl oxide and hydroxyl radical: a theoretical study

The reaction mechanism of carbonyl oxide with hydroxyl radical was investigated by using CASSCF, B3LYP, QCISD, CASPT2, and CCSD(T) theoretical approaches with the 6-311+G(d,p), 6-311+G(2df, 2p), and aug-cc-pVTZ basis sets. This reaction involves the formation of H2CO + HO2 radical in a process that is computed to be exothermic by 57 kcal/mol. However, the reaction mechanism is very complex and begins with the formation of a pre-reactive hydrogen-bonded complex and follows by the addition of HO radical to the carbon atom of H2COO, forming the intermediate peroxy-radical H2C(OO)OH before producing formaldehyde and hydroperoxy radical. Our calculations predict that both the pre-reactive hydrogen-bonded complex and the transition state of the addition process lie energetically below the enthalpy of the separate reactants (DeltaH(298K) = -6.1 and -2.5 kcal/mol, respectively) and the formation of the H2C(OO)OH adduct is exothermic by about 74 kcal/mol. Beyond this addition process, further reaction mechanisms have also been investigated, which involve the abstraction of a hydrogen of carbonyl oxide by HO radical, but the computed activation barriers suggest that they will not contribute to the gas-phase reaction of H2COO + HO.     

The reaction of tricarbon with acetylene: an ab initio/RRKM study of the potential energy surface and product branching ratios

Ab initio calculations of the potential energy surface for the C3(1Sigmag+)+C2H2(1Sigmag+) reaction have been performed at the RCCSD(T)/cc-pVQZ//B3LYP/6-311G(d,p) + ZPE[B3LYP/6-311G(d,p)] level with extrapolation to the complete basis set limit for key intermediates and products. These calculations have been followed by statistical calculations of reaction rate constants and product branching ratios. The results show the reaction to begin with the formation of the 3-(didehydrovinylidene)cyclopropene intermediate i1 or five-member ring isomer i7 with the entrance barriers of 7.6 and 13.8 kcal/mol, respectively. i1 rearranges to the other C5H2 isomers, including ethynylpropadienylidene i2, singlet pentadiynylidene i3, pentatetraenylidene i4, ethynylcyclopropenylidene i5, and four- and five-member ring structures i6, i7, and i8 by ring-closure and ring-opening processes and hydrogen migrations. i2, i3, and i4 lose a hydrogen atom to produce the most stable linear isomer of C5H with the overall reaction endothermicity of approximately 24 kcal/mol. H elimination from i5 leads to the formation of the cyclic C5H isomer, HC2C3, +H, 27 kcal/ mol above C3+C2H2. 1,1-H2 loss from i4 results in the linear pentacarbon C5+H2 products endothermic by 4 kcal/mol. The H elimination pathways occur without exit barriers, whereas the H2 loss from i4 proceeds via a tight transition state 26.4 kcal/mol above the reactants. The characteristic energy threshold for the reaction under single collision conditions is predicted be in the range of approximately 24 kcal/mol. Product branching ratios obtained by solving kinetic equations with individual rate constants calculated using RRKM and VTST theories for collision energies between 25 and 35 kcal/mol show that l-C5H+H are the dominant reaction products, whereas HC2C3+H and l-C5+H2 are minor products with branching ratios not exceeding 2.5% and 0.7%, respectively. The ethynylcyclopropenylidene isomer i5 is calculated to be the most stable C5H2 species, more favorable than triplet pentadiynylidene i3t by approximately 2 kcal/mol.     

Thermodynamic and kinetic studies of H atom transfer from HMo(CO)3(eta(5)-C5H5) to Mo(N[t-Bu]Ar)3 and (PhCN)Mo(N[t-Bu]Ar)3: direct insertion of benzonitrile into the Mo-H bond of HMo(N[t-Bu]Ar)3 forming (Ph(H)C=N)Mo(N[t-Bu]Ar)3

Synthetic studies are reported that show that the reaction of either H2SnR2 (R = Ph, n-Bu) or HMo(CO)3(Cp) (1-H, Cp = eta(5)-C5H5) with Mo(N[t-Bu]Ar)3 (2, Ar = 3,5-C6H3Me2) produce HMo(N[t-Bu]Ar)3 (2-H). The benzonitrile adduct (PhCN)Mo(N[t-Bu]Ar)3 (2-NCPh) reacts rapidly with H2SnR2 or 1-H to produce the ketimide complex (Ph(H)C=N)Mo(N[t-Bu]Ar)3 (2-NC(H)Ph). The X-ray crystal structures of both 2-H and 2-NC(H)Ph are reported. The enthalpy of reaction of 1-H and 2 in toluene solution has been measured by solution calorimetry (DeltaH = -13.1 +/- 0.7 kcal mol(-1)) and used to estimate the Mo-H bond dissociation enthalpy (BDE) in 2-H as 62 kcal mol(-1). The enthalpy of reaction of 1-H and 2-NCPh in toluene solution was determined calorimetrically as DeltaH = -35.1 +/- 2.1 kcal mol(-1). This value combined with the enthalpy of hydrogenation of [Mo(CO)3(Cp)]2 (1(2)) gives an estimated value of 90 kcal mol(-1) for the BDE of the ketimide C-H of 2-NC(H)Ph. These data led to the prediction that formation of 2-NC(H)Ph via nitrile insertion into 2-H would be exothermic by approximately 36 kcal mol(-1), and this reaction was observed experimentally. Stopped flow kinetic studies of the rapid reaction of 1-H with 2-NCPh yielded DeltaH(double dagger) = 11.9 +/- 0.4 kcal mol(-1), DeltaS(double dagger) = -2.7 +/- 1.2 cal K(-1) mol(-1). Corresponding studies with DMo(CO)3(Cp) (1-D) showed a normal kinetic isotope effect with kH/kD approximately 1.6, DeltaH(double dagger) = 13.1 +/- 0.4 kcal mol(-1) and DeltaS(double dagger) = 1.1 +/- 1.6 cal K(-1) mol(-1). Spectroscopic studies of the much slower reaction of 1-H and 2 yielding 2-H and 1/2 1(2) showed generation of variable amounts of a complex proposed to be (Ar[t-Bu]N)3Mo-Mo(CO)3(Cp) (1-2). Complex 1-2 can also be formed in small equilibrium amounts by direct reaction of excess 2 and 1(2). The presence of 1-2 complicates the kinetic picture; however, in the presence of excess 2, the second-order rate constant for H atom transfer from 1-H has been measured: 0.09 +/- 0.01 M(-1) s(-1) at 1.3 degrees C and 0.26 +/- 0.04 M(-1) s(-1) at 17 degrees C. Study of the rate of reaction of 1-D yielded kH/kD = 1.00 +/- 0.05 consistent with an early transition state in which formation of the adduct (Ar[t-Bu]N)3Mo...HMo(CO)3(Cp) is rate limiting.     

Ab initio studies of alkyl radical reactions: Combination and disproportionation reactions of CH3 with C2H5, and the decomposition of chemically activated C3H8

This paper reports the first quantitative ab initio prediction of the disproportionation/combination ratio of alkyl+alkyl reactions using CH3+C2H5 as an example. The reaction has been investigated by the modified Gaussian-2 method with variational transition state or Rice-Ramsperger-Kassel-Marcus calculations for several channels producing (1) CH4+CH2CH2, (2) C3H8, (3) CH4CH3CH, (4) H2+CH3CHCH2, (5) H2+CH3CCH3, and (6) C2H6+CH2 by H-abstraction and association/decomposition mechanisms through singlet and triplet potential energy paths. Significantly, the disproportionation reaction (1) producing CH4+C2H4 was found to occur primarily by the lowest energy path via a loose hydrogen-bonding singlet molecular complex, H3CHC2H4, with a 3.5 kcal/mol binding energy and a small decomposition barrier (1.9 kcal/mol), instead of a direct H-abstraction process. Bimolecular reaction rate constants for the formation of the above products have been calculated in the temperature range 300-3000 K. At 1 atm, formation of C3H8 is dominant below 1200 K. Over 1200 K, the disproportionation reaction becomes competitive. The sum of products (3)-(6) accounts for less than 0.3% below 1500 K and it reaches around 1%-4% above 2000 K. The predicted rate constant for the disproportionation reaction with multiple reflections above the complex well, k1=5.04 x T(0.41) exp(429/T) at 200-600 K and k1=1.96 x 10(-20) T(2.45) exp(1470/T) cm3 molecule(-1) s(-1) at 600-3000 K, agrees closely with experimental values. Similarly, the predicted high-pressure rate constants for the combination reaction forming C3H8 and its reverse dissociation reaction in the temperature range 300-3000 K, k2(infinity)=2.41 x 10(-10) T(-0.34) exp(259/T) cm3 molecule(-1) s(-1) and k(-2)(infinity)=8.89 x 10(22) T(-1.67)exp(-46 037/T) s(-1), respectively, are also in good agreement with available experimental data.     

Thermodynamic and ab initio analysis of the controversial enthalpy of formation of formaldehyde.

There are two values, -26.0 and -27.7 kcal mol(-1), that are routinely reported in literature evaluations for the standard enthalpy of formation, Delta(f) H(o)(298), of formaldehyde (CH(2)=O), where error limits are less than the difference in values. In this study, we summarize the reported literature for formaldehyde enthalpy values based on evaluated measurements and on computational studies. Using experimental reaction enthalpies for a series of reactions involving formaldehyde, in conjunction with known enthalpies of formation, its enthalpy is determined to be -26.05+/-0.42 kcal mol(-1), which we believe is the most accurate enthalpy currently available. For the same reaction series, the reaction enthalpies are evaluated using six computational methods: CBS-Q, CBS-Q//B3, CBS-APNO, G2, G3, and G3B3 yield Delta(f) H(o)(298)=-25.90+/-1.17 kcal mol(-1), which is in good agreement to our experimentally derived result. Furthermore, the computational chemistry methods G3, G3MP2B3, CCSD/6-311+G(2df,p)//B3LYP/6-31G(d), CCSD(T)/6-311+G(2df,p)//B3LYP/6-31G(d), and CBS-APNO in conjunction with isodesmic and homodesmic reactions are used to determine Delta(f) H(o)(298). Results from a series of five work reactions at the higher levels of calculation are -26.30+/-0.39 kcal mol(-1) with G3, -26.45+/-0.38 kcal mol(-1) with G3MP2B3, -26.09+/-0.37 kcal mol(-1) with CBS-APNO, -26.19+/-0.48 kcal mol(-1) with CCSD, and -26.16+/-0.58 kcal mol(-1) with CCSD(T). Results from heat of atomization calculations using seven accurate ab initio methods yields an enthalpy value of -26.82+/-0.99 kcal mol(-1). The results using isodesmic reactions are found to give enthalpies more accurate than both other computational approaches and are of similar accuracy to atomization enthalpy calculations derived from computationally intensive W1 and CBS-APNO methods. Overall, our most accurate calculations provide an enthalpy of formation in the range of -26.2 to -26.7 kcal mol(-1), which is within computational error of the suggested experimental value. The relative merits of each of the three computational methods are discussed and depend upon the accuracy of experimental enthalpies of formation required in the calculations and the importance of systematic computational errors in the work reaction. Our results also calculate Delta(f) H(o)(298) for the formyl anion (HCO(-)) as 1.28+/-0.43 kcal mol(-1).     

Studies of the kinetics and thermochemistry of the forward and reverse reaction Cl + C6H6 = HCl + C6H5

The laser flash photolysis resonance fluorescence technique was used to monitor atomic Cl kinetics. Loss of Cl following photolysis of CCl4 and NaCl was used to determine k(Cl + C6H6) = 6.4 x 10(-12) exp(-18.1 kJ mol(-1)/RT) cm(3) molecule(-1) s(-1) over 578-922 K and k(Cl + C6D6) = 6.2 x 10(-12) exp(-22.8 kJ mol(-1)/RT) cm(3) molecule(-1) s(-1) over 635-922 K. Inclusion of literature data at room temperature leads to a recommendation of k(Cl + C6H6) = 6.1 x 10(-11) exp(-31.6 kJ mol(-1)/RT) cm(3) molecule(-1) s(-1) for 296-922 K. Monitoring growth of Cl during the reaction of phenyl with HCl led to k(C6H5 + HCl) = 1.14 x 10(-12) exp(+5.2 kJ mol(-1)/RT) cm(3) molecule(-1) s(-1) over 294-748 K, k(C6H5 + DCl) = 7.7 x 10(-13) exp(+4.9 kJ mol(-1)/RT) cm(3) molecule(-1) s(-1) over 292-546 K, an approximate k(C6H5 + C6H5I) = 2 x 10(-11) cm(3) molecule(-1) s(-1) over 300-750 K, and an upper limit k(Cl + C6H5I) < or = 5.3 x 10(-12) exp(+2.8 kJ mol(-1)/RT) cm(3) molecule(-1) s(-1) over 300-750 K. Confidence limits are discussed in the text. Third-law analysis of the equilibrium constant yields the bond dissociation enthalpy D(298)(C6H5-H) = 472.1 +/- 2.5 kJ mol(-1) and thus the enthalpy of formation Delta(f)H(298)(C6H5) = 337.0 +/- 2.5 kJ mol(-1).     

Arene-mercury complexes stabilized by gallium chloride: relative rates of H/D and arene exchange

We have previously proposed that the Hg(arene)(2)(GaCl(4))(2) catalyzed H/D exchange reaction of C(6)D(6) with arenes occurs via an electrophilic aromatic substitution reaction in which the coordinated arene protonates the C(6)D(6). To investigate this mechanism, the kinetics of the Hg(C(6)H(5)Me)(2)(GaCl(4))(2) catalyzed H/D exchange reaction of C(6)D(6) with naphthalene has been studied. Separate second-order rate constants were determined for the 1- and 2-positions on naphthalene; that is, the initial rate of H/D exchange = k(1i)[Hg][C-H(1)] + k(2i)[Hg][C-H(2)]. The ratio of k(1i)/k(2i) ranges from 11 to 2.5 over the temperature range studied, commensurate with the proposed electrophilic aromatic substitution reaction. Observation of the reactions over an extended time period shows that the rates change with time, until they again reach a new and constant second-order kinetics regime. The overall form of the rate equation is unchanged: final rate = k(1f)[Hg][C-H(1)] + k(2f)[Hg][C-H(2)]. This change in the H/D exchange is accompanied by ligand exchange between Hg(C(6)D(6))(2)(GaCl(4))(2) and naphthalene to give Hg(C(10)H(8))(2)(GaCl(4))(2,) that has been characterized by (13)C CPMAS NMR and UV-visible spectroscopy. The activation parameters for the ligand exchange may be determined and are indicative of a dissociative reaction and are consistent with our previously calculated bond dissociation for Hg(C(6)H(6))(2)(AlCl(4))(2). The initial Hg(arene)(2)(GaCl(4))(2) catalyzed reaction of naphthalene with C(6)D(6) involves the deuteration of naphthalene by coordinated C(6)D(6); however, as ligand exchange progresses, the pathway for H/D exchange changes to where the protonation of C(6)D(6) by coordinated naphthalene dominates. The site selectivity for the H/D exchange is initially due to the electrophilic aromatic substitution of naphthalene. As ligand exchange occurs, this selectivity is controlled by the activation of the naphthalene C-H bonds by mercury.     

Theoretical study of the C6H3 potential energy surface and rate constants and product branching ratios of the C2H(2Sigma+) + C4H2(1Sigma(g)+) and C4H(2Sigma+) + C2H2(1Sigma(g)+) reactions

Ab initio CCSD(T)cc-pVTZ//B3LYP6-311G(**) and CCSD(T)/complete basis set (CBS) calculations of stationary points on the C(6)H(3) potential energy surface have been performed to investigate the reaction mechanism of C(2)H with diacetylene and C(4)H with acetylene. Totally, 25 different C(6)H(3) isomers and 40 transition states are located and all possible bimolecular decomposition products are also characterized. 1,2,3- and 1,2,4-tridehydrobenzene and H(2)CCCCCCH isomers are found to be the most stable thermodynamically residing 77.2, 75.1, and 75.7 kcal/mol lower in energy than C(2)H + C(4)H(2), respectively, at the CCSD(T)/CBS level of theory. The results show that the most favorable C(2)H + C(4)H(2) entrance channel is C(2)H addition to a terminal carbon of C(4)H(2) producing HCCCHCCCH, 70.2 kcal/mol below the reactants. This adduct loses a hydrogen atom from the nonterminal position to give the HCCCCCCH (triacetylene) product exothermic by 29.7 kcal/mol via an exit barrier of 5.3 kcal/mol. Based on Rice-Ramsperger-Kassel-Marcus calculations under single-collision conditions, triacetylene+H are concluded to be the only reaction products, with more than 98% of them formed directly from HCCCHCCCH. The C(2)H + C(4)H(2) reaction rate constants calculated by employing canonical variational transition state theory are found to be similar to those for the related C(2)H + C(2)H(2) reaction in the order of magnitude of 10(-10) cm(3) molecule(-1) s(-1) for T = 298-63 K, and to show a negative temperature dependence at low T. A general mechanism for the growth of polyyne chains involving C(2)H + H(C[triple bond]C)(n)H --> H(C[triple bond]C)(n+1)H + H reactions has been suggested based on a comparison of the reactions of ethynyl radical with acetylene and diacetylene. The C(4)H + C(2)H(2) reaction is also predicted to readily produce triacetylene + H via barrierless C(4)H addition to acetylene, followed by H elimination.     

Effect of geminal substitution at silicon on 1-sila- and 1,3-disilacyclobutanes' strain energies, their 2+2 cycloreversion enthalpies, and Si=C pi-bond energies in silenes.

To evaluate the effect of geminal substitution at silicon on 1-sila- and 1,3-disilacyclobutanes' strain energies, their 2+2 cycloreversion enthalpies, and Si=C pi-bond energies in silenes, an ab initio MO study of silenes, R2Si=CH2 (1), 1-silacyclobutanes, cyclo-R2Si(CH2)3 (2), and 1,3-disilacyclobutanes, cyclo-(R2SiCH2)2 (3), was performed using the level of theory denoted MP4/TZ(d)//MP2/6-31G(d) (TZ means the 6-311G(d) basis set for elements of the second period and hydrogen, and the McLean-Chandler (12s,9p)/[6s,5p](d) basis set for the third period elements). In the series R = H, CH3, SiH3, CH3O, NH2, Cl, F, the growth of the reaction enthalpies and strain energies is proportional to the substituents' electronegativities. 2+2 cycloreversion of 2 is endothermic by 40.6-63.1 kcal/mol, whereas that of 3 is endothermic by 72.7-114.2 kcal/mol. On going from a silicon to a fluorine substituent at the sp2-hybridized silicon atom, the pi-bond energy in 1 weakens by 11.3 kcal/mol, and the Si=C bond length shortens by 0.053 A. The effect of substituents' electronegativities at the double-bonded silicon atom in silenes is formulated as follows: the higher electronegativity, the shorter and the weaker the Si=C pi-bond. The latter is rationalized in terms of more strained geometry resulting from the energetic cost for planarizing the R2SiC moiety. The enthalpies of the ring-opening reaction are 68.0-80.1 kcal/mol (a cleavage of the Si-C bond in 3), 65.0-76.4 kcal/mol (a cleavage of the Si-C bond in 2), and 58.0-64.9 kcal/mol (a cleavage of the C-C bond in 2). The pronounced difference in the enthalpies of 2+2 cycloreversion of 1-sila- and 1,3-disilacyclobutanes is mainly due to the difference in the enthalpies of diradicals' decomposition. The decomposition of diradicals resulting from a cleavage of C-C and Si-C bonds in 2 is exothermic by 24.3-3.3 kcal/mol (apart from the difluoro derivative which is endothermic by 5.1 kcal/mol) and 27.0-13.3 kcal/mol, respectively. The decomposition of a 1,4-diradical resulting from ring opening of 3, apart from the disilyl derivative, is the endothermic process for which the enthalpy varies from 10.6 to 40.4 kcal/mol.     

Ab initio and direct dynamics studies of the reaction of singlet methylene with acetylene and the lifetime of the cyclopropene complex

The energetics of the (1)CH(2) + C(2)H(2) --> H + C(3)H(3) reaction are accurately calculated using an extrapolated coupled-cluster/complete basis set (CBS) method based on the cc-pVDZ, cc-pVTZ, and cc-pVQZ basis sets. The reaction enthalpy (0 K) is predicted to be -20.33 kcal/mol. This reaction has no classical barrier in either the entrance or exit channel. However, there are several stable intermediates-cyclopropene (c-C(3)H(4)), allene (CH(2)CCH(2)), and propyne (CH(3)CCH)-along the minimum energy path. These intermediates with zero-point energy corrections lie below the reactants by 87.11 (c-C(3)H(4)), 109.69 (CH(2)CCH(2)), and 110.78 kcal/mol (CH(3)CCH). The vibrationally adiabatic ground-state (VAG) barrier height for c-C(3)H(4) isomerization to allene is obtained as 45.2 kcal/mol, and to propyne as 37.2 kcal/mol. In addition, the (1)CH(2) + C(2)H(2) reaction is investigated utilizing the dual-level "scaling all correlation" (SAC) ab initio method of Truhlar et al., i.e., the UCCSD(SAC)/cc-pVDZ theory. Results show that the reaction occurs via long-lived complexes. The lifetime of the cyclopropene intermediate is obtained as 3.2 +/- 0.4 ps. It is found that the intermediate propyne can be formed directly from reactants through the insertion of (1)CH(2) into a C-H bond of C(2)H(2). However, compared to the major mechanism in which the propyne is produced through a ring-opening of the cyclopropene complex, this reaction pathway is much less favorable. Finally, the theoretical thermal rate constant exhibits a negative temperature dependence, which is in excellent agreement with the previous results. The temperature dependence is consistent with the earlier RRKM results but weaker than the experimental observations at high temperatures.