Weston Thatcher Borden

Transition-State Spectroscopy of Cyclooctatetraene

The 351-nanometer photoelectron spectrum of the planar cyclooctatetraene radical anion (COT·−) shows transitions to two electronic states of cyclooctatetraene (COT). These states correspond to the D4h 1A1g state, which is the transition state for COT ring inversion, and the D8h 3A2u state. The electron binding energy of the 1A1g transition state is 1.099 ± 0.010 electron volts, which is lower by 12.1 ± 0.3 kilocalories per mole than that of the 3A2u state. The photoelectron spectrum shows that the singlet lies well below the triplet in D8h COT and confirms ab initio predictions that the molecule violates Hunds rule. Vibrational structure is observed for both features and is readily assigned by use of a simple potential energy surface.

The lowest singlet and triplet states of the oxyallyl diradical

Small S-T splitting : The photoelectron spectrum of the oxyallyl radical anion (see picture) reveals that the electronic ground state of oxyallyl is singlet, and the lowest triplet state is separated from the singlet state by only (55 ± 2) meV in adiabatic energy.

Qualitative Methods for Predicting the Ground States of Non-Kekule Hydrocarbons and the Effects of Heteroatom Substitution on the Ordering of the Electronic States

Abstract Classification of the NBMOs of a non-Kekule hydrocarbon as being disjoint or non-disjoint can be used to predict the spin of the ground state and the magnitude of the energy difference between it and the lowest excited state. If the NBMOs are non-disjoint, the bonding in the lowest excited states will be more localized than that in the ground state. The nature of the localized pi bonding in the lowest excited states allows one to predict qualitatively which will be most stabilized by hetero-atom substitution and whether it is possible that the attendant stabilization, relative to the ground state, is capable of giving the substituted molecule a ground state of different spin multiplicity. The same predictions can also be made using VB theory.

Experimental evidence for heavy-atom tunneling in the ring-opening of cyclopropylcarbinyl radical from intramolecular 12C/13C kinetic isotope effects.

The intramolecular (13)C kinetic isotope effects for the ring-opening of cyclopropylcarbinyl radical were determined over a broad temperature range. The observed isotope effects are unprecedentedly large, ranging from 1.062 at 80 degrees C to 1.163 at -100 degrees C. Semiclassical calculations employing canonical variational transition-state theory drastically underpredict the observed isotope effects, but the predicted isotope effects including tunneling by a small-curvature tunneling model match well with experiment. These results and a curvature in the Arrhenius plot of the isotope effects support the recently predicted importance of heavy-atom tunneling in cyclopropylcarbinyl ring-opening.

Nitroxyl radical plus hydroxylamine pseudo self-exchange reactions: tunneling in hydrogen atom transfer.

Bimolecular rate constants have been measured for reactions that involve hydrogen atom transfer (HAT) from hydroxylamines to nitroxyl radicals, using the stable radicals TEMPO(*) (2,2,6,6-tetramethylpiperidine-1-oxyl radical), 4-oxo-TEMPO(*) (2,2,6,6-tetramethyl-4-oxo-piperidine-1-oxyl radical), di-tert-butylnitroxyl ((t)Bu(2)NO(*)), and the hydroxylamines TEMPO-H, 4-oxo-TEMPO-H, 4-MeO-TEMPO-H (2,2,6,6-tetramethyl-N-hydroxy-4-methoxy-piperidine), and (t)Bu(2)NOH. The reactions have been monitored by UV-vis stopped-flow methods, using the different optical spectra of the nitroxyl radicals. The HAT reactions all have |DeltaG (o)| < or = 1.4 kcal mol(-1) and therefore are close to self-exchange reactions. The reaction of 4-oxo-TEMPO(*) + TEMPO-H --> 4-oxo-TEMPO-H + TEMPO(*) occurs with k(2H,MeCN) = 10 +/- 1 M(-1) s(-1) in MeCN at 298 K (K(2H,MeCN) = 4.5 +/- 1.8). Surprisingly, the rate constant for the analogous deuterium atom transfer reaction is much slower: k(2D,MeCN) = 0.44 +/- 0.05 M(-1) s(-1) with k(2H,MeCN)/k(2D,MeCN) = 23 +/- 3 at 298 K. The same large kinetic isotope effect (KIE) is found in CH(2)Cl(2), 23 +/- 4, suggesting that the large KIE is not caused by solvent dynamics or hydrogen bonding to solvent. The related reaction of 4-oxo-TEMPO(*) with 4-MeO-TEMPO-H(D) also has a large KIE, k(3H)/k(3D) = 21 +/- 3 in MeCN. For these three reactions, the E(aD) - E(aH) values, between 0.3 +/- 0.6 and 1.3 +/- 0.6 kcal mol(-1), and the log(A(H)/A(D)) values, between 0.5 +/- 0.7 and 1.1 +/- 0.6, indicate that hydrogen tunneling plays an important role. The related reaction of (t)Bu(2)NO(*) + TEMPO-H(D) in MeCN has a large KIE, 16 +/- 3 in MeCN, and very unusual isotopic activation parameters, E(aD) - E(aH) = -2.6 +/- 0.4 and log(A(H)/A(D)) = 3.1 +/- 0.6. Computational studies, using POLYRATE, also indicate substantial tunneling in the (CH(3))(2)NO(*) + (CH(3))(2)NOH model reaction for the experimental self-exchange processes. Additional calculations on TEMPO((*)/H), (t)Bu(2)NO((*)/H), and Ph(2)NO((*)/H) self-exchange reactions reveal why the phenyl groups make the last of these reactions several orders of magnitude faster than the first two. By inference, the calculations also suggest why tunneling appears to be more important in the self-exchange reactions of dialkylhydroxylamines than of arylhydroxylamines.

The potential surface for planar cyclopropenyl radical and anion

The potential surfaces for the 2E″ state of planar cyclopropenyl and the 1E′ state of planar cyclopropenyl anion are examined using full pi‐space configuration interaction within an STO‐3G basis. Both states are subject to first order Jahn–Teller distortions of the bond lengths. Small second order effects slightly favor the ethylenic form of the radical. Much larger second order effects strongly favor the allylic form of the anion.

Calculations Predict Rapid Tunneling by Carbon from the Vibrational Ground State in the Ring Opening of Cyclopropylcarbinyl Radical at Cryogenic Temperatures

B3LYP/6-31G(d) calculations have been performed on the ring opening of cyclopropylcarbinyl radical 1 to 3-buten-1-yl radical 2. The dynamics of the reaction have been computed with canonical variational transition state theory (CVT), both with and without inclusion of small-curvature tunneling (SCT). The CVT + SCT calculations predict that 1 should undergo rapid and temperature-independent ring opening to 2 at cryogenic temperatures, by tunneling from the lowest vibrational level of 1.

RHF and two-configuration SCF calculations are inappropriate for conjugated diradicals

Abstract Restricted Hartee Fock (RHF) and two-configuration self-consistent field (TCSCF) calculations provide qualitatively correct molecular orbitals for the two open-shell electrons in diradicals. Nevertheless, these calculations fail to give correct relative energies and in some cases they even lead to incorrect geometries. Examples of these failures are given for both singlet and triplet states of some conjugated diradicals. In several cases these failures are related to the “doublet instability problem” in RHF calculations on radicals. It is argued that unrestricted Hartee-Fock (UHF) calculations on triplet states are more likely that RHF to provide accurate geometries.

The singlet and triplet state rotational potential surfaces for dihydroxycarbene

Potential surfaces have been computed for rotation of the OH groups in C(OH)2 for both the lowest singlet and triplet state. The minima on the singlet surface occur at planar geometries, which represent maxima on the triplet surface. This result is interpreted in terms of different modes of pi electron donation from oxygen being favored in the two states. Evidence is presented that shows pi electron donation is chiefly responsible for making dihydroxycarbene a ground state singlet.

Calculations predict that carbon tunneling allows the degenerate cope rearrangement of semibullvalene to occur rapidly at cryogenic temperatures.

Calculations on the role of tunneling in the degenerate Cope rearrangements of semibullvalene (1) and barbaralane (3) predict that, at temperatures below 40 K, tunneling from the lowest vibrational level should make the temperature-independent rate constants k = 1.43 x 10(-3) s(-1) and k = 7.28 x 10(-9) s(-1), respectively. An experiment, using semibullvalene-2(4)-d(1), is proposed to test the prediction of rapid tunneling by 1 at cryogenic temperatures.