John Brauman
J.G. Jackson and C.J. Wood Professor of Chemistry, Emeritus
Web page: http://www-chem.stanford.edu/group/brauman/group/john.html
Bio
John Brauman’s research has advanced the understanding of the factors that determine the rates and products of chemical reactions. His primary areas of effort have involved the spectroscopy, photochemistry, reaction dynamics, and reaction mechanisms of gas-phase ions.
John I. Brauman was born in Pittsburgh, PA in 1937. He attended the Massachusetts Institute of Technology (S.B. 1959) and the University of California at Berkeley (Ph.D. 1963). Following a National Science Foundation Postdoctoral Fellowship at the University of California, Los Angeles, he accepted a position at Stanford University where he is now J. G. Jackson - C. J. Wood Professor of Chemistry Emeritus, and serves as Associate Dean of Research. He was previously Department Chair and Associate Dean for Natural Sciences.
Brauman’s work has been recognized in the National Medal of Science, National Academy of Sciences Award in Chemical Sciences, Linus Pauling Medal, Dean's Award for Distinguished Teaching from Stanford University, among many other honors. He is a member of the National Academy of Sciences, American Academy of Arts and Sciences, American Philosophical Society, a Fellow of the American Association for the Advancement of Science, Fellow of the American Chemical Society, and Honorary Fellow of the California Academy of Sciences. He received the 2017 ACS Parsons Award in recognition of his service to public science communication and policy, which includes roles as Deputy Editor for Physical Sciences and Editorial Board Chair for Science magazine, and Home Secretary of the National Academy of Sciences.
Research in the Brauman Group centered on structure and reactivity. Brauman has studied ionic reactions in the gas phase, including acid-base chemistry, the mechanisms of proton transfers, nucleophilic displacement, and addition-elimination reactions. His work has explored the shape of the potential surfaces and the dynamics of reactions on these surfaces. He has made contributions to the field of electron photodetachment spectroscopy of negative ions, measurements of electron affinities, the study of dipole-supported electronic states, and multiple photon infrared activation of ions. He has also studied mechanisms of solution and gas phase organic reactions as well as organometallic reactions and the behavior of biomimetic organometallic species.
Administrative Appointments
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Associate Dean of Research, Dean of Research, Stanford University (2005 - Present)
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Associate Dean for Natural Sciences, Humanities and Sciences, Stanford University (1999 - 2003)
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Chair, Stanford University Department of Chemistry (1995 - 1996)
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Chair, Stanford University Department of Chemistry (1979 - 1983)
Honors & Awards
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National Medal of Science, President of the United States (2002)
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Award in Chemical Sciences, National Academy of Sciences (2001)
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Charles Lathrop Parsons Award, American Chemical Society (2017)
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Willard Gibbs Medal, Chicago Section of the American Chemical Society (2003)
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Linus Pauling Award, Puget Sound, Oregon and Portland Sections of the American Chemical Society (2002)
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James Flack Norris Award in Physical Organic Chemistry, American Chemical Society (1986)
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Award in Pure Chemistry, American Chemical Society (1973)
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Member, National Academy of Sciences (1976)
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Member, American Philosophical Society (2004)
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Fellow, American Chemical Society (2011)
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D. Sc. Honoris Causa,, The Scripps Research Institute (2009)
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Honorary Fellow, California Academy of Sciences (1991)
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Arthur C. Cope Scholar Award, American Chemical Society (1986)
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R.C. Fuson Award, University of Nevada, Reno (1986)
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Fellow, American Association for the Advancement of Science (1980)
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Guggenheim Fellow, John Simon Guggenheim Memorial Foundation (1978)
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Dean's Award for Distinguished Teaching, Stanford University (1976)
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Harrison Howe Award, Rochester Section of the American Chemical Society (1976)
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Member, American Academy of Arts and Sciences (1976)
Boards, Advisory Committees, Professional Organizations
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Camille and Henry Dreyfus Foundation, Board of Directors (2006 - Present)
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Committee of Selection, John Simon Guggenheim Memorial Foundation (2004 - 2014)
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Home Secretary, National Academy of Sciences (2003 - 2011)
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Chair, Senior Editorial Board, AAAS Science (2001 - 2011)
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Annual Reviews, Board of Directors (2000 - Present)
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Board of Trustees, Gordon Research Conferences (1991 - 1995)
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Member of Council, Gordon Research Conferences (1989 - 1995)
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Deputy Editor for Physical Sciences, AAAS Science (1985 - 2000)
Professional Education
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SB, Massachusetts Institute of Technology, Chemistry (1959)
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PhD, University of California at Berkeley, Chemistry (1963)
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NSF Postdoctoral Fellow, University of California at Los Angeles, Chemistry (1963)
All Publications
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Geometry Dependence of the Ring-Opening E2 Reaction in Lactones
JOURNAL OF PHYSICAL CHEMISTRY A
2010; 114 (3): 1392-1397
Abstract
Gas phase bimolecular elimination reactions (E2) of lactones, with and without alkyl substitution on the omega carbon, have been studied. The comparison between the substituted and corresponding unsubstituted lactones reveals, without complications from ring strain, the effect of geometric distortion from the periplanar geometry preferred for E2 reactions. The four- and five-membered ring lactones show a significant effect from the distortion, while the six- and seven-membered rings show relatively little. The geometric distortion is clearly much more important than the ring strain. The kinetic energy dependence of the E2 reaction as well as the proton transfer reaction between fluoride and a partially deuterated delta-valerolactone has also been investigated.
View details for DOI 10.1021/jp906968d
View details for Web of Science ID 000273672600022
View details for PubMedID 19860403
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Steric and Solvation Effects in Ionic S(N)2 Reactions
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
2009; 131 (44): 16162-16170
Abstract
This paper explores the contribution of solvation to the overall steric effects of S(N)2 reactions observed in solution. The reactions of chloride ion with a series of alkyl chloronitriles, RCH(CN)Cl (R = methyl, ethyl, isopropyl, tert-butyl) were investigated both experimentally and theoretically. These reactions serve as a model system for the parent reactions, Cl(-) + RCH(2)Cl, which are too slow to measure. Each additional substitution at the beta-carbon lowers the reactivity, clearly demonstrating a steric hindrance effect. The magnitude of the steric effect, however, is not significantly different in the gas phase and in solution. We conclude that the solvation energies of the corresponding S(N)2 transition states must be similar regardless of size of the substituent. This lack of size dependence in the current system is in sharp contrast with many other ionic systems such as ionization of simple alkyl alcohols, where solvation depends strongly on size. We propose that the weak size dependence results from the compensation between a direct shielding effect of the substituent and an indirect ionic solvation effect, which arises from the geometric perturbations introduced by the substitution. The conclusion is further supported by calculations using polarizable continuum models and QM/MM simulations.
View details for DOI 10.1021/ja9053459
View details for Web of Science ID 000271513700050
View details for PubMedID 19842649
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Hydrogen Bonding Lowers Intrinsic Nucleophilicity of Solvated Nucleophiles
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
2008; 130 (45): 15038-15046
Abstract
The relationship between nucleophilicity and the structure/environment of the nucleophile is of fundamental importance in organic chemistry. In this work, we have measured nucleophilicities of a series of substituted alkoxides in the gas phase. The functional group substitutions affect the nucleophiles through ion-dipole, ion-induced dipole interactions and through hydrogen bonding whenever structurally possible. This set of alkoxides serves as an ideal model system for studying nucleophiles under microsolvation settings. Marcus theory was applied to analyze the results. Using Marcus theory, we separate nucleophilicity into two independent components, an intrinsic nucleophilicity and a thermodynamic driving force determined solely by the overall reaction exothermicity. It is found that the apparent nucleophilicities of the substituted alkoxides are always much lower than those of the unsubstituted ones. However, ion-dipole, ion-induced dipole interactions, by themselves, do not significantly affect the intrinsic nucleophilicity; the decrease in the apparent nucleophilicity results from a weaker thermodynamic driving force. On the other hand, hydrogen bonding not only stabilizes the nucleophile but also increases the intrinsic barrier height by 3 to approximately 4 kcal mol (-1). In this regard, the hydrogen bond is not acting as a perturbation in the sense of an external dipole but more directly affects the electronic structure and reactivity of the nucleophilic alkoxide. This finding offers a deeper insight into the solvation effect on nucleophilicity, such as the remarkably lower reactivities in nucleophilic substitution reactions in protic solvents than in aprotic solvents.
View details for DOI 10.1021/ja802814a
View details for Web of Science ID 000260682300045
View details for PubMedID 18928286
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Chemistry - Not so simple
SCIENCE
2008; 319 (5860): 168-168
View details for DOI 10.1126/science.1152387
View details for Web of Science ID 000252246400029
View details for PubMedID 18187647
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Vinyl hydrogen acidities of two stereoisomers
JOURNAL OF PHYSICAL CHEMISTRY A
2007; 111 (7): 1362-1367
Abstract
The gas-phase acidities of the vinyl hydrogens of cis- and trans-2-butene were measured by the silane kinetic method in a Fourier-transform ion cyclotron resonance spectrometer. The acidities of ethene and the secondary vinyl hydrogen of propene were measured by the same method. The method was calibrated using the known acidities of methane and benzene. The vinyl hydrogens of trans-2-butene are more acidic than the vinyl hydrogens of cis-2-butene by 4.5 kcal/mol; the acidities of ethene and the secondary vinyl hydrogen of propene are between those of the two butenes. The acidity of cis-2-butene is 409 +/- 2 kcal/mol, and the acidity of trans-2-butene is 405 +/- 2 kcal/mol. Density functional theory calculations are in good agreement with the experiments. The results are discussed in terms of steric interactions, polarizabilities, dipole-dipole interactions, and charge-dipole interactions.
View details for DOI 10.1021/jp0666075
View details for Web of Science ID 000244225000026
View details for PubMedID 17256827
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Kinetics of (porphyrin)manganese(III)-catalyzed olefin epoxidation with a soluble iodosylbenzene derivative
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
2006: 2707-2714
View details for DOI 10.1002/ejoc.200600079
View details for Web of Science ID 000238601500005
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Enolate structure and electron affinity
JOURNAL OF PHYSICAL CHEMISTRY A
2005; 109 (39): 8785-8793
Abstract
Photodetachment cross sections for a series of cyclic enolates were measured using a continuous wave (CW) ion cyclotron resonance instrument to generate and detect the ions. We report electron affinities for the radicals corresponding to the removal of the extra electron from the following anions: 2-methylcyclopent-1-enolate, 3-methylcyclopent-1-enolate, 4-methylcyclopent-1-enolate, 5-methylcyclopent-1-enolate, 2-methylcyclohex-1-enolate, 3-methylcyclohex-1-enolate, 4-methylcyclohex-1-enolate, 4-ethylcyclohex-1-enolate, 5-methylcyclohex-1-enolate, and 6-methylcyclohex-1-enolate. Some of these anions are mixed with their tautomers, derived from deprotonation of the parent ketone; the consequences of this are analyzed. The effect of alkylation on the electron affinities is discussed. The effect of vibrational modes on the lifetimes of the dipole-bound states of 4-methylcyclohex-1-enolate and 4-ethylcyclohex-1-enolate is discussed.
View details for DOI 10.1021/jp050024y
View details for Web of Science ID 000232314200014
View details for PubMedID 16834281
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Molecular rotations and dipole-bound state lifetimes
JOURNAL OF PHYSICAL CHEMISTRY A
2005; 109 (39): 8794-8799
Abstract
A computational model based on classical molecular rotation provides insight into the observability of dipole-bound states. The observability is related to the lifetime of the state prior to rotational autodetachment of the electron. The model tracks an ensemble of dipole-bound states. Their motion in space is integrated as a function of time, which provides a means to analyze the lifetimes of the dipole-bound states. The results are generally in good agreement with experimental data. Some exceptions show the limitations of the model but also provide insight into the autodetachment mechanism.
View details for DOI 10.1021/jp050025q
View details for Web of Science ID 000232314200015
View details for PubMedID 16834282
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Proton exchange and transesterification reactions of acetate enolates with alcohols in the gas phase
JOURNAL OF PHYSICAL CHEMISTRY A
2005; 109 (38): 8553-8559
Abstract
Transesterification reactions and proton exchange reactions between acetate enolates and alcohols were studied both separately and together. Kinetic analysis shows that transesterification and proton exchange happen in a single collision event. The transesterification reaction is best viewed as an endothermic proton transfer, followed by an exchange of alkoxide and an exothermic proton transfer. Reaction barriers were modeled by Rice-Ramsperger-Kassel-Marcus theory and compared to quantum calculations. CBS-QB3 achieves good agreement whereas B3LYP and MP2 give slightly higher barriers. Quantum calculations also predict that the transition state for these transesterification reactions is the same as that for direct transesterification reactions between alkoxides and esters.
View details for DOI 10.1021/jp0527305
View details for Web of Science ID 000232121300015
View details for PubMedID 16834253
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Acidities in cyclohexanediols enhanced by intramolecular hydrogen bonds
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
2004; 126 (39): 12614-12620
Abstract
Equilibrium gas-phase acidities of the six isomeric cyclohexanediols were measured in a Fourier transform ion cyclotron resonance mass spectrometer. Although all six cyclohexanediols have the same functional groups and similar structures, the acidities vary over 11 kcal/mol. This large difference is due mostly to the balance between hydrogen bonding and geometric strain. To understand the origins of the acidity differences in more detail, the conformations and energetics of the cyclohexanediols were studied using density functional theory, which gave good agreement with the experimental acidities. Finally, methanol-methoxide and methanol-methanol interactions were used as a model for the hydrogen bonding.
View details for DOI 10.1021/ja049780s
View details for Web of Science ID 000224219900081
View details for PubMedID 15453794
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Radical autoxidation and autogenous O-2 evolution in manganese-porphyrin catalyzed alkane oxidations with chlorite
INORGANIC CHEMISTRY
2004; 43 (17): 5198-5204
Abstract
A manganese porphyrin catalyst employing chlorite (ClO(2)(-)) as a "shunt" oxidant displays remarkable activity in alkane oxidation, oxidizing cyclohexane to cyclohexanol and cyclohexanone with >800 turnover numbers. The ketone is apparently formed without the intermediacy of alcohol and accounts for an unusually large fraction of the product ( approximately 40%). Radical scavenging experiments indicate that the alkane oxidation mechanism involves both carbon-centered and oxygen-centered radicals. The carbon-radical trap CBrCl(3) completely suppresses cyclohexanone formation and reduces cyclohexanol turnovers, while the oxygen-radical trap Ph(2)NH inhibits all oxidation until it is consumed. These observations are indicative of an autoxidation mechanism, a scenario further supported by TEMPO inhibition and (18)O(2) incorporation into products. However, similar cyclohexane oxidation activity occurs when air is excluded. This is explained by mass spectrometric and volumetric measurements showing catalyst-dependent O(2) evolution from the reaction mixture. The catalytic disproportionation of ClO(2)(-) into Cl(-) and O(2) provides sufficient O(2) to support an autoxidation mechanism. A two-path oxidation scheme is proposed to explain all of the experimental observations. The first pathway involves manganese-porphyrin catalyzed decomposition of ClO(2)(-) into both O(2) and an unidentified radical initiator, leading to classical autoxidation chemistry providing equal amounts of cyclohexanol and cyclohexanone. The second pathway is a "rebound" oxygenation involving a high-valent manganese-oxo intermediate, accounting for the excess of alcohol over ketone. This system highlights the importance of mechanistic studies in catalytic oxidations with highly reactive oxidants, and it is unusual in its ability to sustain autoxidation even under apparent exclusion of O(2).
View details for DOI 10.1021/ic049922j
View details for Web of Science ID 000223397100009
View details for PubMedID 15310195
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Steric retardation of S(N)2 reactions in the gas phase and solution
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
2004; 126 (29): 9054-9058
Abstract
The gas-phase S(N)2 reactions of chloride with ethyl and neopentyl chlorides and their alpha-cyano derivatives have been explored with B3LYP, CBS-QB3, and PDDG/PM3 calculations. Calculations predict that the steric effect of the tert-butyl group raises the activation energy by about 6 kcal/mol relative to methyl in both cases. Solvent effects have been computed with QM/MM Monte Carlo simulations for DMSO, methanol, and water, as well as with a polarizable continuum model, CPCM. Solvents cause a large increase in the activation energies of these reactions but have a very small differential effect on the ethyl and neopentyl substrates and their cyano derivatives. The theoretical results contrast with previous conclusions that were based upon gas-phase rate measurements.
View details for DOI 10.1021/ja049070m
View details for Web of Science ID 000222855300045
View details for PubMedID 15264838
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Donor ligand effect on the nature of the oxygenating species in Mn-III(salen)-catalyzed epoxidation of olefins: Experimental evidence for multiple active oxidants
INORGANIC CHEMISTRY
2004; 43 (8): 2672-2679
Abstract
The stereoselectivity of olefin epoxidation catalyzed by Mn(III)(salen)X (1a, X = Cl(-); 1b, X = BF(4)(-)) complexes is examined in the presence of neutral donor ligands, employing various iodosylarenes (ArIO: PhIO, C(6)F(5)IO, and MesIO) as the oxygen atom source. The cis/trans ratios of stilbene oxides and the enantiomeric excesses of styrene oxide and 1,2-dihydronaphthalene oxide are found to be strongly dependent on the nature of the iodosylarenes under certain conditions. In other cases, olefin epoxidation is shown to proceed with essentially identical diastereoselectivities or enantioselectivities, regardless of the oxygen atom source used. We propose that a Mn(V)(salen)-oxo intermediate and a complex between the catalyst and the terminal oxidant competitively effect the epoxidation when the stereoselectivities are markedly dependent on the oxygen atom source. A single Mn(V)(salen)-oxo species is considered to be the sole oxygenating intermediate when the terminal oxidants do not exert a notable influence on the product selectivities. Our results clearly demonstrate the existence of multiple oxidizing species and the conditions in which only a single oxygenating intermediate is involved. The axial donor ligands (both anionic ligands and neutral ligands) are shown to strongly influence both the identity and the reactivity of the oxygenating species.
View details for DOI 10.1021/ic035360c
View details for Web of Science ID 000220838400030
View details for PubMedID 15074985
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Dynamics of competitive reactions: Endothermic proton transfer and exothermic substitution
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
2004; 126 (8): 2640-2646
Abstract
Dynamics of an endothermic proton-transfer reaction, F(-) with dimethyl sulfoxide, and an endothermic proton-transfer reaction with a competing exothermic substitution (S(N)2) channel, F(-) with borane-methyl sulfide complex, were investigated using a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR) and kinetic modeling. The two proton-transfer reactions have slightly positive and a small negative overall free energy changes, respectively. Energy-dependent rate constants were measured as a function of F(-) ion translational energy, and the resulting kinetics were modeled with the RRKM (Rice-Ramsperger-Kassel-Marcus) theory. The observed rate constants for the proton-transfer reactions of F(-) with dimethyl sulfoxide and with borane-methyl sulfide complex are identical, with a value of 0.17 x 10(-9) cm(3) molecule(-1) s(-1); for the S(N)2 reaction, k = 0.90 x 10(-9) cm(3) molecule(-1) s(-1) at 350 K. Both proton-transfer reactions have positive entropy changes in the forward direction and show positive energy dependences. The competing S(N)2 reaction exhibits negative energy dependence and becomes less important at higher energies. The changes of the observed rate constants agree with RRKM theory predictions for a few kcal/mol of additional kinetic energy. The dynamic change of the branching ratio for the competing proton transfer and the substitution reactions results from the competition between the microscopic rate constants associated with each channel.
View details for Web of Science ID 000189279700073
View details for PubMedID 14982474
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Determination of the acidity of long chain alcohols using infrared multiple photon dissociation
JOURNAL OF PHYSICAL CHEMISTRY A
2002; 106 (51): 12299-12304
View details for Web of Science ID 000179984900015
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Conformation-dependent reaction thermochemistry: Study of lactones and lactone enolates in the gas phase
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
2002; 124 (18): 5213-5221
Abstract
Gas-phase acidities (Delta H degrees (acid)) of lactones with ring sizes from four to seven have been measured on a Fourier transform ion cyclotron resonance mass spectrometer. Electron affinities (EAs) of the corresponding lactone enolate radicals were measured on a continuous-wave ion cyclotron resonance mass spectrometer, and the bond dissociation energies (BDEs) of the alpha C-H bonds were derived. In order of increasing ring size, Delta H degrees (acid) = 368.7 +/- 2., 369.4 +/- 2.2, 367.3 +/- 2.2, and 368.3 +/- 2.2 kcal/mol and BDE = 99.4 +/- 2.3, 94.8 +/- 2.3, 89.2 +/- 2.3, and 92.8 +/- 2.4 kcal/mol for beta-propiolactone, gamma-butyrolactone, delta-valerolactone, and epsilon-caprolactone, respectively. For their corresponding enolate radicals, EA = 44.1 +/- 0.3, 38.8 +/- 0.3, 35.3 +/- 0.3, and 37.9 +/- 0.6 kcal/mol. All of these lactones are considerably more acidic than methyl acetate, consistent with a dipole repulsion model. Both BDEs and EAs show a strong dependence on ring size, whereas Delta H degrees (acid) does not. These findings are discussed, taking into account differential electronic effects and differential strain between the reactant and product species in each reaction.
View details for DOI 10.1021/ja011897i
View details for Web of Science ID 000175369100049
View details for PubMedID 11982386
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Energy deposition in S(N)2 reaction products and kinetic energy effects on reactivity
JOURNAL OF PHYSICAL CHEMISTRY A
2002; 106 (15): 3804-3813
View details for DOI 10.1021/jp0141070
View details for Web of Science ID 000175164400024
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Steric effects and solvent effects in ionic reactions
SCIENCE
2002; 295 (5563): 2245-2247
Abstract
Rates of SN2 reactions of chloride ion with methyl- and tert-butyl-substituted chloroacetonitrile were measured by using Fourier transform-ion cyclotron resonance spectrometry to follow the isotopic exchange reaction. Barrier heights for these reactions indicate that steric effects in the gas phase are diminished relative to apparent steric effects in solution. We attribute the increased barrier in solution to a solvation effect. Monte Carlo simulations done using statistical perturbation theory confirm that steric hindrance to solvation contributes to SN2 barriers in solution.
View details for Web of Science ID 000174561700038
View details for PubMedID 11910104
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Mechanism of dihydrogen cleavage by high-valent metal oxo compounds: Experimental and computational studies
INORGANIC CHEMISTRY
2001; 40 (24): 6272-6280
Abstract
The oxidation of dihydrogen by metal tetraoxo compounds was investigated. Kinetic measurements of the oxidations of H(2) by MnO(4)(-) and RuO(4), performed by UV-vis spectroscopy, showed these reactions to be quite rapid at 25 degrees C (k(1) approximately (3-6) x 10(-2) M(-1) s(-1)). Rates measured for H(2) oxidation by MnO(4)(-) in aqueous solution (using KMnO(4)) and in chlorobenzene (using (n)Bu(4)NMnO(4)) revealed only a minor solvent effect on the reaction rate. Substantial kinetic isotope effects [(k(H)2/k(D)2 = 3.8(2) (MnO(4)(-), aq), 4.5(5) (MnO(4)(-), C(6)H(5)Cl soln), and 1.8(6) (RuO(4), CCl(4) soln)] indicated that H-H bond cleavage is rate determining and that the mechanism of dihydrogen cleavage is likely similar in aqueous and organic solutions. Third-row transition-metal oxo compounds, such as OsO(4), ReO(4)(-), and MeReO(3), were found to be completely unreactive toward H(2). Experiments were performed to probe for a catalytic hydrogen/deuterium exchange between D(2) and H(2)O as possible evidence of dihydrogen sigma-complex intermediates, but no H/D exchange was observed in the presence of various metal oxo compounds at various pH values. In addition, no inhibition of RuO(4)-catalyzed hydrocarbon oxidation by H(2) was observed. On the basis of the available evidence, a concerted mechanism for the cleavage of H(2) by metal tetraoxo compounds is proposed. Theoretical models were developed for pertinent MnO(4)(-) + H(2) transition states using density functional theory in order to differentiate between concerted [2 + 2] and [3 + 2] scissions of H(2). The density functional theory calculations strongly favor the [3 + 2] mechanism and show that the H(2) cleavage shares some mechanistic features with related hydrocarbon oxidation reactions. The calculated activation energy for the [3 + 2] pathway (DeltaH(++) = 15.4 kcal mol(-1)) is within 2 kcal mol(-1) of the experimental value.
View details for DOI 10.1021/ic010639j
View details for Web of Science ID 000172181400028
View details for PubMedID 11703130
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The RS-center dot HSR hydrogen bond: Acidities of alpha,omega-dithiols and electron affinities of their monoradicals
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
2001; 123 (40): 9800-9805
Abstract
Gas-phase acidities (deltaGo(acid)) have been measured for 1,2-ethanedithiol, 1,3-propanedithiol, and 1,4-butanedithiol, using a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. Adiabatic electron affinities (EAs) of the thiolate monoradicals of these compounds were assigned from electron photodetachment spectra of their corresponding thiolate monoanions, acquired using a cw-ICR. The dithiols exhibit enhanced acidities (up to 8.7 kcal/mol in deltaGo(acid)) and greater EAs (up to 6.7 kcal/mol) than analogous monothiol species. These differences are attributed to an intramolecular RS-.HSR hydrogen bond in the thiolate anion. Considerations of the RO-.HOR hydrogen bond in monoanions of alpha,omega-diols and in the [CH(3)O-.HOCH(3)] complex anion suggest that the RS-.HSR hydrogen bond provides up to 9 kcal/mol extra stabilization.
View details for DOI 10.1021/ja0039684
View details for Web of Science ID 000171508600009
View details for PubMedID 11583541
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Multiple active oxidants in cytochrome P-450 model oxidations
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
2000; 122 (45): 11098-11100
View details for Web of Science ID 000165337800008
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Energetics and mechanism of alkyl cleavage transition states: Relative gas-phase acidities of alkanes
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
2000; 122 (44): 10878-10885
View details for Web of Science ID 000165385700016
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Twist and fluoresce
SCIENCE
2000; 290 (5490): 286-287
View details for Web of Science ID 000089818100031
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Competitive reaction of axial ligands during biomimetic oxygenations
INORGANIC CHEMISTRY
2000; 39 (20): 4625-4629
View details for DOI 10.1021/ic000071z
View details for Web of Science ID 000089707500034
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Unusual ionic hydrogen bonds: Complexes of acetylides and fluoroform
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
2000; 122 (36): 8739-8745
View details for DOI 10.1021/ja000806z
View details for Web of Science ID 000089432300020
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Hydrogen-bonded complexes of methanol and acetylides. Structure and energy correlations
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
2000; 122 (22): 5371-5378
View details for Web of Science ID 000087540500016
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Direct observation of spin forbidden proton-transfer reactions: (NO-)-N-3+HA ->(HNO)-H-1+A(-)
JOURNAL OF PHYSICAL CHEMISTRY A
2000; 104 (9): 1795-1798
View details for Web of Science ID 000085770400001
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Negative ion electron photodetachment from a near-blackbody photon source
JOURNAL OF PHYSICAL CHEMISTRY A
2000; 104 (6): 1117-1120
View details for Web of Science ID 000085393600006
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Translational energy dependence and potential energy surfaces of gas phase S(N)2 and addition-elimination reactions
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1999; 121 (50): 11790-11797
View details for Web of Science ID 000084512700025
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A quantitative UV-VIS probe of enantioselectivity in metalloporphyrin catalyzed oxygenation using aluminium model complexes
CHEMICAL COMMUNICATIONS
1999: 1783-1784
View details for Web of Science ID 000082585000002
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Intramolecular microsolvation of S(N)2 transition states
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1999; 121 (28): 6690-6699
View details for Web of Science ID 000081603000019
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Intrinsic structure-reactivity relationships in gas-phase transacylation reactions: Identity exchange of substituted benzoyl chlorides with chloride ion
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1999; 121 (11): 2508-2515
View details for Web of Science ID 000079363300022
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Nonstatistical reactivity in a vibrationally excited S(N)2 intermediate
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1998; 120 (46): 12125-12126
View details for Web of Science ID 000077210900034
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Fulvio Cacace: Note of appreciation
INTERNATIONAL JOURNAL OF MASS SPECTROMETRY
1998; 180: XIX-XIX
View details for Web of Science ID 000077101400003
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Acidity, basicity, and the stability of hydrogen bonds: Complexes of RO-+HCF3
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1998; 120 (42): 10863-10870
View details for Web of Science ID 000076693100009
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alpha-stabilization by silyl and phosphino substitution
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1998; 120 (12): 2919-2924
View details for Web of Science ID 000072892800027
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Gas-phase ionic reactions: Dynamics and mechanism of nucleophilic displacements
SCIENCE
1998; 279 (5358): 1882-1886
View details for Web of Science ID 000072613300033
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An agostic alternative to the P-450 rebound mechanism
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1998; 120 (2): 425-426
View details for Web of Science ID 000071624500025
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[FHNO](-): An intermediate in a spin-forbidden proton transfer reaction
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1997; 119 (48): 11697-11698
View details for Web of Science ID A1997YK50200022
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Gas-phase ionic reactions of benzyl and methoxide anions
JOURNAL OF PHYSICAL ORGANIC CHEMISTRY
1997; 10 (7): 531-536
View details for Web of Science ID A1997XW11600007
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Phase-shifting acceleration of ions in an ion cyclotron resonance spectrometer: Kinetic energy distribution and reaction dynamics
JOURNAL OF PHYSICAL CHEMISTRY A
1997; 101 (26): 4745-4752
View details for Web of Science ID A1997XG93500013
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Perturbed equilibria and statistical energy redistribution in a gas-phase S(N)2 reaction
SCIENCE
1997; 276 (5318): 1536-1538
View details for Web of Science ID A1997XC70100034
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Aza-crown-capped porphyrin models of myoglobin: Studies of the steric interactions of gas binding
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1997; 119 (15): 3481-3489
View details for Web of Science ID A1997WU27200009
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Cyclopentadienyl, indenyl, and fluorenyl anions: Gas-phase and solvation energy contributions to electron detachment energies
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1997; 119 (9): 2249-2254
View details for Web of Science ID A1997WL64600024
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Unimolecular dynamics in bimolecular ion-molecule reactions
Discussion Meeting of the Deutsche-Bunsen-Gesellschaft on Unimolecular Reactions
WILEY-V C H VERLAG GMBH. 1997: 510–15
View details for Web of Science ID A1997WR85400024
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Electron photodetachment spectroscopy of (E)- and (Z)-propionaldehyde enolate anions. Electron affinities of the stereoisomers of propionaldehyde enolate radicals
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1997; 119 (8): 2054-2055
View details for Web of Science ID A1997WK42200030
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Branching ratios in activated systems
JOURNAL OF PHYSICAL CHEMISTRY A
1997; 101 (1): 19-24
View details for Web of Science ID A1997WL08000004
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Generation and chemistry of fluorinated acetoxyl and oxyallyl biradical anions (distonic radical anions) in the gas phase
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1996; 118 (49): 12432-12436
View details for Web of Science ID A1996VX65400020
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Electron photodetachment spectroscopy of solvated anions: RO center dot HF- or ROH center dot F-?
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1996; 118 (49): 12424-12431
View details for Web of Science ID A1996VX65400019
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Catalytic activation of H-2 and C-H bonds by electron-deficient ruthenium(II) porphyrins
INORGANIC CHEMISTRY
1996; 35 (23): 6746-6754
View details for Web of Science ID A1996VR79800022
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Intramolecular microsolvation of thermoneutral gas-phase S(N)2 reactions
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1996; 118 (28): 6786-6787
View details for Web of Science ID A1996UX67300034
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Alkyl substituent effect in the deprotonation of unsymmetrical ketones
JOURNAL OF PHYSICAL CHEMISTRY
1996; 100 (21): 8827-8835
View details for Web of Science ID A1996UM67700032
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Rearrangement and fragmentation mechanisms of vibrationally activated enolate ions in the gas phase
JOURNAL OF PHYSICAL CHEMISTRY
1996; 100 (18): 7471-7479
View details for Web of Science ID A1996UJ11700024
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Ambident reactivity of enolate anions in the gas phase. Experimental determination of carbon vs oxygen acylation with CF3COCl
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1996; 118 (3): 636-641
View details for Web of Science ID A1996TR63300014
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Gas-phase nucleophilic displacement reactions
JOURNAL OF MASS SPECTROMETRY
1995; 30 (12): 1653-1662
View details for Web of Science ID A1995TK61600003
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1,3-HYDROGEN REARRANGEMENTS OF VIBRATIONALLY ACTIVATED ENOLATE IONS IN THE GAS-PHASE
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1995; 117 (40): 10088-10092
View details for Web of Science ID A1995RZ83800020
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ELECTRON-AFFINITIES AND GAS-PHASE ACIDITIES OF ORGANOGERMANIUM AND ORGANOTIN COMPOUNDS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1995; 117 (17): 4905-4910
View details for Web of Science ID A1995QW14000022
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THROUGH THE GLASS LIGHTLY
SCIENCE
1995; 267 (5204): 1609-1618
View details for Web of Science ID A1995QM39700026
View details for PubMedID 7886446
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THREITOL-STRAPPED MANGANESE PORPHYRINS AS ENANTIOSELECTIVE EPOXIDATION CATALYSTS OF UNFUNCTIONALIZED OLEFINS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1995; 117 (2): 692-703
View details for Web of Science ID A1995QC77600013
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THE S(N)2 IDENTITY EXCHANGE-REACTION F-+CH3F-]FCH3+F- - DEFINITIVE AB-INITIO PREDICTIONS
JOURNAL OF PHYSICAL CHEMISTRY
1994; 98 (51): 13532-13540
View details for Web of Science ID A1994PY49100018
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DIRECT EXPERIMENTAL-EVIDENCE FOR A MULTIPLE WELL POTENTIAL-ENERGY SURFACE IN A GAS-PHASE EXOTHERMIC CARBONYL ADDITION-ELIMINATION REACTION
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1994; 116 (20): 9216-9221
View details for Web of Science ID A1994PK97900043
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ALPHA-SILYL-SUBSTITUENT STABILIZATION OF CARBANIONS AND SILYL ANIONS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1994; 116 (18): 8304-8310
View details for Web of Science ID A1994PF91300042
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DIOXYGEN BINDING IN IRON AND COBALT PICNIC BASKET PORPHYRINS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1994; 116 (14): 6245-6251
View details for Web of Science ID A1994NX54800026
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INTERMEDIATES AND POTENTIAL-ENERGY SURFACES IN THERMONEUTRAL CARBONYL ADDITION-ELIMINATION REACTIONS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1994; 116 (13): 5839-5846
View details for Web of Science ID A1994NV42100039
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INTRINSIC STRUCTURE-REACTIVITY RELATIONSHIPS IN GAS-PHASE S(N)2 REACTIONS - IDENTITY EXCHANGE OF SUBSTITUTED BENZYL CHLORIDES WITH CHLORIDE-ION
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1994; 116 (6): 2471-2480
View details for Web of Science ID A1994NE02600030
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BOUND EXCITED ELECTRONIC STATES OF ANIONS
JOURNAL OF CHEMICAL PHYSICS
1994; 100 (3): 1840-1848
View details for Web of Science ID A1994MU31600006
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THE PROTON-TRANSFER SURFACE OF CH3OHF-
JOURNAL OF CHEMICAL PHYSICS
1994; 100 (3): 2058-2088
View details for Web of Science ID A1994MU31600030
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APPLICATION OF MARCUS THEORY TO GAS-PHASE SN2 REACTIONS - EXPERIMENTAL SUPPORT OF THE MARCUS THEORY ADDITIVITY POSTULATE
JOURNAL OF PHYSICAL CHEMISTRY
1993; 97 (50): 13158-13164
View details for Web of Science ID A1993MN05200023
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GAS-PHASE PROTON-TRANSFER AND SUBSTITUTION-REACTIONS - ENERGY-DEPENDENCE AND DISSOCIATION DYNAMICS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1993; 115 (23): 10823-10829
View details for Web of Science ID A1993MH75200045
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MOLECULAR ROTATION AND THE OBSERVATION OF DIPOLE-BOUND STATES OF ANIONS
JOURNAL OF CHEMICAL PHYSICS
1993; 99 (10): 7586-7594
View details for Web of Science ID A1993MH74400031
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REGIOSELECTIVE AND ENANTIOSELECTIVE EPOXIDATION CATALYZED BY METALLOPORPHYRINS
SCIENCE
1993; 261 (5127): 1404-1411
Abstract
Recent progress in regioselective and enantioselective epoxidations catalyzed by metalloporphyrins is discussed here, with an explanation of the biomimetic antecedents of this area and its relevance to synthetic applications. Classification of the catalysts that have been studied allows useful conclusions to be drawn about the development of this field. In particular, both the most promising biomimetic and practical catalysts have arisen from systems that can be systematically modified by convenient synthetic methodology.
View details for Web of Science ID A1993LW54900022
View details for PubMedID 8367724
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ASYMMETRIC EPOXIDATION CATALYZED BY AN IRON BINAP CAPPED PORPHYRIN
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS
1992: 1647-1649
View details for Web of Science ID A1992JY81600015
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THE SN2 IDENTITY EXCHANGE-REACTION CLCH2CN + CL--]CL- + CLCH2CN - EXPERIMENT AND THEORY
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1992; 114 (23): 9136-9153
View details for Web of Science ID A1992JW79700055
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INFRARED MULTIPLE PHOTON STUDIES OF ALKOXIDE ALCOHOL COMPLEXES
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1992; 114 (14): 5733-5741
View details for Web of Science ID A1992JB98000037
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ELECTRON PHOTODETACHMENT FROM ORGANOPHOSPHIDE IONS - ELECTRON-AFFINITIES AND SUBSTITUENT EFFECTS IN ORGANOPHOSPHINES AND THEIR CONJUGATE RADICALS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1992; 114 (12): 4737-4743
View details for Web of Science ID A1992HX81500041
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KINETIC-MODELS FOR GAS-PHASE ELECTRON-TRANSFER REACTIONS BETWEEN NITROBENZENES
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1992; 114 (3): 887-893
View details for Web of Science ID A1992HB53700014
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SHAPE-SELECTIVE OLEFIN EPOXIDATION CATALYZED BY METALLO PICNIC-BASKET PORPHYRINS
SYMP ON HOMOGENEOUS TRANSITION METAL CATALYZED REACTIONS, AT THE 199TH NATIONAL MEETING OF THE AMERICAN CHEMICAL SOC
AMER CHEMICAL SOC. 1992: 153–162
View details for Web of Science ID A1992BW97Q00010
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SHAPE-SELECTIVE OLEFIN EPOXIDATION CATALYZED BY METALLO PICNIC-BASKET PORPHYRINS
ADVANCES IN CHEMISTRY SERIES <D>
1992: 153-162
View details for Web of Science ID A1992JZ41000010
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ADDITION AND DEPROTONATION IN REACTIONS OF HYDROXIDE ION WITH A BETA-HYDROXYSILANE
INTERNATIONAL JOURNAL OF MASS SPECTROMETRY
1991; 109: 1-14
View details for Web of Science ID A1991GN86600002
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GAS-PHASE PROTON-TRANSFER REACTIONS BETWEEN ALKOXIDE ANIONS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1991; 113 (16): 5942-5949
View details for Web of Science ID A1991FZ53300004
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REACTION DYNAMICS ON BARRIERLESS REACTION SURFACES - A MODEL FOR ISOERGIC GAS-PHASE PROTON-TRANSFER REACTIONS
JOURNAL OF CHEMICAL PHYSICS
1991; 94 (11): 7164-7180
View details for Web of Science ID A1991FL83700023
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ROTATIONAL ENHANCEMENT OF THE PROTON-TRANSFER BARRIER FOR ION-MOLECULE REACTIONS ON A DOUBLE-MINIMUM SURFACE
CHEMICAL PHYSICS LETTERS
1991; 177 (3): 326-330
View details for Web of Science ID A1991EZ55900019
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HEMIACETAL ANIONS - A MODEL FOR TETRAHEDRAL REACTION INTERMEDIATES
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1991; 113 (3): 805-812
View details for Web of Science ID A1991EW17800012
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MECHANISTIC STUDIES OF OLEFIN EPOXIDATION BY A MANGANESE PORPHYRIN AND HYPOCHLORITE - AN ALTERNATIVE EXPLANATION OF SATURATION KINETICS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1990; 112 (22): 7980-7984
View details for Web of Science ID A1990EE66300020
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FRAGMENT ISOTOPE DISTRIBUTION AS A SIGNATURE OF MOLECULAR FLUXIONALITY
CHEMICAL PHYSICS LETTERS
1990; 172 (3-4): 231-234
View details for Web of Science ID A1990DZ50500008
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DISSOCIATION AND VIBRATION-INDUCED ELECTRON AUTODETACHMENT OF 3-FLUORONITROBENZENE RADICAL-ANION BY INFRARED MULTIPLE PHOTON EXCITATION
JOURNAL OF PHYSICAL CHEMISTRY
1990; 94 (9): 3403-3415
View details for Web of Science ID A1990DB98800013
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ELECTRON-ATTACHMENT CHEMISTRY OF SICL4 - RELEVANCE TO PLASMA REACTIONS
INTERNATIONAL JOURNAL OF MASS SPECTROMETRY AND ION PROCESSES
1990; 96 (3): 299-307
View details for Web of Science ID A1990DA56500006
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SUICIDE INACTIVATION OF CYTOCHROME-P-450 MODEL COMPOUNDS BY TERMINAL OLEFINS .2. STERIC AND ELECTRONIC EFFECTS IN HEME N-ALKYLATION AND EPOXIDATION
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1990; 112 (8): 2986-2998
View details for Web of Science ID A1990CY82600022
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SUICIDE INACTIVATION OF CYTOCHROME-P-450 MODEL COMPOUNDS BY TERMINAL OLEFINS .1. A MECHANISTIC STUDY OF HEME N-ALKYLATION AND EPOXIDATION
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1990; 112 (8): 2977-2986
View details for Web of Science ID A1990CY82600021
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ON THE MECHANISTIC DEPENDENCE OF THE AFFINITY DECAY
JOURNAL OF CHEMICAL PHYSICS
1990; 92 (6): 3569-3578
View details for Web of Science ID A1990CU65800031
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GAS-PHASE PROTON-TRANSFER FROM TOLUENES TO BENZYL ANIONS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1989; 111 (17): 6491-6496
View details for Web of Science ID A1989AM21600002
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GAS-PHASE ACIDITIES OF ORGANOSILANES AND ELECTRON-AFFINITIES OF ORGANOSILYL RADICALS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1989; 111 (11): 3835-3841
View details for Web of Science ID A1989U736700013
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VIBRATIONALLY INDUCED ELECTRON DETACHMENT - A RATE FOR ELECTRON LOSS FROM VIBRATIONALLY EXCITED ACETONE ENOLATE ANION
JOURNAL OF PHYSICAL CHEMISTRY
1989; 93 (1): 61-68
View details for Web of Science ID A1989R914400018
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ROTATIONAL STRUCTURE IN AN EXCITED VIBRONIC BAND OF THE DIPOLE-SUPPORTED STATE OF CYANOMETHYL ANION, CH2CN-
JOURNAL OF CHEMICAL PHYSICS
1989; 90 (1): 68-73
View details for Web of Science ID A1989R629500011
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QUANTITATIVE MEASURE OF ALPHA-SILYL CARBANION STABILIZATION - THE ELECTRON-AFFINITY OF (TRIMETHYLSILYL)METHYL RADICAL
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1988; 110 (25): 8333-8336
View details for Web of Science ID A1988R339800008
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INFRARED MULTIPLE-PHOTON DECOMPOSITION OF [CH3OHF]- AND C6H5CH2-
JOURNAL OF PHYSICAL CHEMISTRY
1988; 92 (24): 6948-6953
View details for Web of Science ID A1988R227300022
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ADVANCES IN INSTRUMENTATION
SCIENCE
1988; 242 (4876): 165-165
View details for Web of Science ID A1988Q436800001
View details for PubMedID 17787639
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CARBON AND PROTON BASICITY
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1988; 110 (17): 5611-5613
View details for Web of Science ID A1988P764900002
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ELECTRON-TRANSFER COMPETES WITH PROTON-TRANSFER IN GAS-PHASE ACID-BASE REACTIONS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1988; 110 (12): 4048-4049
View details for Web of Science ID A1988N751500059
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SPECTROSCOPY AND DYNAMICS OF THE DIPOLE-SUPPORTED STATE OF ACETYL FLUORIDE ENOLATE ANION
JOURNAL OF CHEMICAL PHYSICS
1988; 88 (11): 6785-6792
View details for Web of Science ID A1988N666400012
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SYNTHESIS, CHARACTERIZATION, AND X-RAY STRUCTURE OF THE RUTHENIUM PICNIC-BASKET PORPHYRINS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1988; 110 (11): 3477-3486
View details for Web of Science ID A1988N634100023
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REVERSIBLE BINDING OF DINITROGEN AND DIOXYGEN BY A RUTHENIUM PICNIC-BASKET PORPHYRIN
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1988; 110 (11): 3486-3495
View details for Web of Science ID A1988N634100024
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MECHANISTIC STUDIES OF GAS-PHASE NEGATIVE-ION UNIMOLECULAR DECOMPOSITIONS - ALKOXIDE ANIONS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1988; 110 (9): 2714-2722
View details for Web of Science ID A1988N319800003
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FRONTIERS IN CHEMISTRY
SCIENCE
1988; 240 (4851): 373-373
View details for Web of Science ID A1988N019200001
View details for PubMedID 17784056
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AN INVESTIGATION OF THE MECHANISM OF NON-PHOTOCHEMICAL HOLE BURNING OF RESORUFIN IN ETHANOL GLASS
CHEMICAL PHYSICS LETTERS
1988; 143 (1): 1-5
View details for Web of Science ID A1988L560100001
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MANGANESE PICNIC BASKET PORPHYRINS - CYTOCHROME-P-450 ACTIVE-SITE ANALOGS
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
1988; 61 (1): 47-57
View details for Web of Science ID A1988M800600007
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EFFECT OF HYDROGEN-BOND STRENGTH ON RESORUFIN NONPHOTOCHEMICAL HOLE BURNING IN ETHANOL-2,2,2-TRIFLUOROETHANOL GLASSES
CHEMICAL PHYSICS LETTERS
1987; 142 (5): 371-375
View details for Web of Science ID A1987L138900015
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PHOTODISSOCIATION SPECTROSCOPY OF THE NEGATIVE-ION DIMER OF TOLUQUINONE
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1987; 109 (25): 7591-7597
View details for Web of Science ID A1987L283800001
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CAPACITANCE BRIDGE DETECTOR AND SIGNAL LOCK FOR ION-CYCLOTRON RESONANCE SPECTROMETRY
REVIEW OF SCIENTIFIC INSTRUMENTS
1987; 58 (8): 1460-1463
View details for Web of Science ID A1987J607600021
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ELECTRON PHOTODETACHMENT SPECTROSCOPY OF TRAPPED NEGATIVE-IONS
CHEMICAL REVIEWS
1987; 87 (3): 607-622
View details for Web of Science ID A1987H812200008
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SPECTROSCOPY OF REACTIVE INTERMEDIATES - ELECTRON PHOTODETACHMENT FROM SOLVATED ANIONS
JOURNAL OF CHEMICAL PHYSICS
1987; 86 (10): 5350-5357
View details for Web of Science ID A1987H434600016
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PHOTOCHEMISTRY OF AQUEOUS PERMANGANATE ION
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1987; 109 (10): 3003-3010
View details for Web of Science ID A1987H284300023
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MATERIALS SCIENCE
SCIENCE
1987; 235 (4792): 953-953
View details for Web of Science ID A1987G168200001
View details for PubMedID 17782221
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A STEPWISE MECHANISM FOR GAS-PHASE UNIMOLECULAR ION DECOMPOSITIONS - ISOTOPE EFFECTS IN THE FRAGMENTATION OF TERT-BUTOXIDE ANION
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1987; 109 (4): 961-970
View details for Web of Science ID A1987G075700001
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INVOLVEMENT OF CYANIDE IN THE REGULATION OF ETHYLENE BIOSYNTHESIS
PLANT PHYSIOLOGY AND BIOCHEMISTRY
1987; 25 (1): 55-61
View details for Web of Science ID A1987G734500008
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INTRINSIC NUCLEOPHILICITY
ADVANCES IN CHEMISTRY SERIES
1987: 23-33
View details for Web of Science ID A1987G382400002
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MARCUS THEORY APPLIED TO REACTIONS WITH DOUBLE-MINIMUM POTENTIAL SURFACES
JOURNAL OF PHYSICAL CHEMISTRY
1986; 90 (16): 3559-3562
View details for Web of Science ID A1986D481400021
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A DIPOLE-SUPPORTED STATE IN CYANOMETHYL ANION, THE CONJUGATE BASE OF ACETONITRILE - ROTATIONAL BAND ASSIGNMENTS IN THE ELECTRON PHOTODETACHMENT SPECTRUM OF-CH2CN
JOURNAL OF CHEMICAL PHYSICS
1986; 84 (10): 5284-5289
View details for Web of Science ID A1986C330800007
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DIMETHYLSILANONE ENOLATE ANION - COMPETITIVE FRAGMENTATION AND ELECTRON AUTODETACHMENT OF VIBRATIONALLY EXCITED SILOXIDE ANIONS IN THE GAS-PHASE
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1986; 108 (10): 2541-2546
View details for Web of Science ID A1986C377800009
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OXYGENATION OF STYRENE BY CYTOCHROME-P-450 MODEL SYSTEM - A MECHANISTIC STUDY
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1986; 108 (10): 2588-2594
View details for Web of Science ID A1986C377800016
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2-PULSE 2-LASER PHOTODISSOCIATIONS OF MOLECULAR-IONS - COLLISIONAL RELAXATION OF BROMO-3-(TRIFLUOROMETHYL)-BENZENE CATION
JOURNAL OF CHEMICAL PHYSICS
1986; 84 (7): 3870-3881
View details for Web of Science ID A1986A517600038
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COMPETING CHANNELS IN INFRARED MULTIPLE PHOTON DECOMPOSITION
INTERNATIONAL JOURNAL OF CHEMICAL KINETICS
1986; 18 (3): 379-398
View details for Web of Science ID A1986A636500009
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COMPUTERS
SCIENCE
1986; 231 (4741): 905-905
View details for Web of Science ID A1986A067700001
View details for PubMedID 17740277
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REACTIONS OF A RHODIUM(I) MACROCYCLE WITH ORGANIC DIHALIDES - OXIDATIVE-ADDITION AND BETA-ELIMINATION PATHWAYS
ORGANOMETALLICS
1986; 5 (2): 218-222
View details for Web of Science ID A1986A079100008
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RHODIUM(III)-TO-RHODIUM(I) ALKYL TRANSFER - A RHODIUM MACROCYCLE WHICH IS BOTH NUCLEOPHILE AND LEAVING GROUP
ORGANOMETALLICS
1986; 5 (2): 215-218
View details for Web of Science ID A1986A079100007
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OXIDATIVE ADDITION MECHANISMS OF A 4-COORDINATE RHODIUM(I) MACROCYCLE
ORGANOMETALLICS
1986; 5 (2): 310-322
View details for Web of Science ID A1986A079100022
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STRUCTURE AND REACTIVITY IN IONIC REACTIONS
JOURNAL OF PHYSICAL CHEMISTRY
1986; 90 (3): 471-477
View details for Web of Science ID A1986AYZ4100025
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ELECTRON PHOTODETACHMENT SPECTROSCOPY OF SOLVATED ANIONS - A PROBE OF STRUCTURE AND ENERGETICS
CHEMICAL PHYSICS LETTERS
1985; 118 (1): 38-39
View details for Web of Science ID A1985AMN3600009
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MECHANISTIC INFORMATION FROM INFRARED MULTIPLE PHOTON DECOMPOSITION - THE ETHYLISOPROPYLAMINE PROTON-TRANSFER SYSTEM
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1985; 107 (4): 761-765
View details for Web of Science ID A1985ACC4700004
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EXPERIMENTAL AND THEORETICAL INVESTIGATION OF THE AZIDE ANION (N-3-) IN THE GAS-PHASE
BERICHTE DER BUNSEN-GESELLSCHAFT-PHYSICAL CHEMISTRY CHEMICAL PHYSICS
1985; 89 (10): 1026-1031
View details for Web of Science ID A1985ATW1000001
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EPOXIDATION OF OLEFINS BY CYTOCHROME-P-450 MODEL COMPOUNDS - KINETICS AND STEREOCHEMISTRY OF OXYGEN ATOM TRANSFER AND ORIGIN OF SHAPE SELECTIVITY
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1985; 107 (7): 2000-2005
View details for Web of Science ID A1985AFA6200034
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GAS-PHASE ION CHEMISTRY
SCIENCE
1985; 227 (4689): 863-869
Abstract
Progress has been made in the understanding of potential energy surfaces for unimolecular ion dissociations and ion-molecule reactions. With recent advances in instrumentation, many new techniques have been developed to generate and study ions, ion-molecule complexes, and large ionic clusters. Developments in ion spectroscopy have enabled considerable advances to be made in the determination of ion structures.
View details for Web of Science ID A1985ABT5400010
View details for PubMedID 17821216
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PRODUCT BRANCHING IN INFRARED MULTIPLE PHOTON DECOMPOSITION OF GAS-PHASE IONS - MECHANISTIC IMPLICATIONS FOR PROTON-TRANSFER REACTIONS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1985; 107 (7): 1934-1940
View details for Web of Science ID A1985AFA6200023
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ELECTRON PHOTODETACHMENT FROM PHENYLNITRENE, ANILIDE, AND BENZYL ANIONS - ELECTRON-AFFINITIES OF THE ANILINO AND BENZYL RADICALS AND PHENYLNITRENE
JOURNAL OF PHYSICAL CHEMISTRY
1984; 88 (22): 5285-5290
View details for Web of Science ID A1984TQ16000035
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EPOXIDATION OF OLEFINS BY CYTOCHROME-P-450 MODEL COMPOUNDS - MECHANISM OF OXYGEN ATOM TRANSFER
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA-PHYSICAL SCIENCES
1984; 81 (10): 3245-3248
Abstract
The mechanism of the Mn(III) porphyrin-catalyzed epoxidation of olefins by lithium hypochlorite is examined. The active oxidant is thought to be a high-valent manganese-oxo complex. It is shown that a relatively stable intermediate is reversibly formed upon interaction of the olefin and the oxo complex. The decomposition of this intermediate to Mn(III) porphyrin and epoxide is the rate-determining step of the catalytic cycle. Some analogies to the biochemical epoxidation of olefins catalyzed by cytochrome P-450 are discussed.
View details for Web of Science ID A1984SU47900001
View details for PubMedID 6587349
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A DETERMINATION OF THE TRIPLET SINGLET SPLITTING IN PHENYLNITRENE VIA PHOTODETACHMENT SPECTROSCOPY
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1984; 106 (12): 3443-3446
View details for Web of Science ID A1984SV60800010
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ENTROPY BOTTLENECKS IN ION MOLECULE REACTIONS
JOURNAL OF CHEMICAL PHYSICS
1984; 80 (5): 1894-1899
View details for Web of Science ID A1984SH43200024
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INFRARED MULTIPLE PHOTON PHOTOCHEMISTRY OF GAS-PHASE IONS
ISRAEL JOURNAL OF CHEMISTRY
1984; 24 (3): 223-231
View details for Web of Science ID A1984TP61900010
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DYNAMICS AND REACTION-MECHANISMS OF ORGANIC IONS IN THE GAS-PHASE
PURE AND APPLIED CHEMISTRY
1984; 56 (12): 1809-1818
View details for Web of Science ID A1984TU20400013
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SPECTROSCOPY AND DYNAMICS OF THE DIPOLE-BOUND STATE OF ACETALDEHYDE ENOLATE
JOURNAL OF CHEMICAL PHYSICS
1984; 81 (11): 4883-4892
View details for Web of Science ID A1984TX68900022
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O-2 AND CO BINDING TO IRON(II) PORPHYRINS - A COMPARISON OF THE PICKET FENCE AND POCKET PORPHYRINS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1983; 105 (10): 3052-3064
View details for Web of Science ID A1983QQ61100019
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GAS-PHASE ACID-BASE CHEMISTRY
ANNUAL REVIEW OF PHYSICAL CHEMISTRY
1983; 34: 187-215
View details for Web of Science ID A1983RN94700009
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INTRINSIC BARRIERS IN NUCLEOPHILIC DISPLACEMENTS - A GENERAL-MODEL FOR INTRINSIC NUCLEOPHILICITY TOWARD METHYL CENTERS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1983; 105 (9): 2672-2680
View details for Web of Science ID A1983QN29200026
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A SILICA-SUPPORTED RHODIUM HYDROFORMYLATION CATALYST - EVIDENCE FOR DINUCLEAR ELIMINATION
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1983; 105 (25): 7288-7294
View details for Web of Science ID A1983RU76100014
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MULTIPLE DECOMPOSITION PATHWAYS IN INFRARED MULTIPLE-PHOTON-INDUCED REACTIONS OF IONS
CHEMICAL PHYSICS LETTERS
1983; 98 (1): 1-5
View details for Web of Science ID A1983QW52700001
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SYNTHESIS AND CHARACTERIZATION OF THE POCKET PORPHYRINS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1983; 105 (10): 3038-3052
View details for Web of Science ID A1983QQ61100018
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MECHANISTIC ASPECTS OF A HOMOGENEOUS CARBON-MONOXIDE HYDROGENATION CATALYST-IR4(CO)12 IN MOLTEN ALCL3-NACL
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1983; 105 (12): 3913-3922
View details for Web of Science ID A1983QU52200029
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EFFECT OF AXIAL BASE ON DIOXYGEN AND CARBON-MONOXIDE AFFINITIES OF IRON(II) PORPHYRINS - IMIDAZOLE VS PYRIDINE
INORGANIC CHEMISTRY
1983; 22 (10): 1427-1432
View details for Web of Science ID A1983QQ49400003
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INFRARED MULTI-PHOTON PHOTODETACHMENT OF NEGATIVE-IONS IN THE GAS-PHASE
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1982; 104 (3): 663-667
View details for Web of Science ID A1982NA88300005
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INFRARED PHOTOCHEMISTRY OF [(C2H5)2O]2H+ AND C3F6+ - A COMPARISON OF PULSED AND CONTINUOUS-WAVE LASER PHOTO-DISSOCIATION METHODS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1982; 104 (3): 652-658
View details for Web of Science ID A1982NA88300003
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NUCLEOPHILIC-SUBSTITUTION
ACS SYMPOSIUM SERIES
1982; 198: 81-102
View details for Web of Science ID A1982PJ02800004
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PHOTO-DISSOCIATION OF STILBENE RADICAL CATION
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1982; 104 (6): 1483-1486
View details for Web of Science ID A1982NG33500006
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INFRARED MULTI-PHOTON DISSOCIATION OF THE METHANOL SOLVATE OF THE FLUORIDE-ION, CH3OHF-
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1982; 104 (3): 658-663
View details for Web of Science ID A1982NA88300004
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ELECTRON PHOTODETACHMENT STUDY OF SULFUR-HEXAFLUORIDE ANION - COMMENTS ON THE STRUCTURE OF SF6-
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1982; 104 (1): 13-19
View details for Web of Science ID A1982MX40800004
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PROTON-TRANSFER REACTIONS BETWEEN 9-ALKYLFLUORENE AND (9-ALKYLFLUORENYL)LITHIUM IN ETHER
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1982; 104 (2): 600-610
View details for Web of Science ID A1982MZ48700038
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RATES OF PROTON ABSTRACTION FROM CONJUGATED DIENES IN THE GAS-PHASE
HELVETICA CHIMICA ACTA
1981; 64 (4): 1058-1062
View details for Web of Science ID A1981LW54000010
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PHOTODETACHMENT OF THE AZIDE ANION IN THE GAS-PHASE - ELECTRON-AFFINITY OF THE AZIDE RADICAL
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1981; 103 (7): 1802-1805
View details for Web of Science ID A1981LK27100037
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ELECTRON PHOTODETACHMENT FROM HS- - THE ELECTRON-AFFINITY OF HS
PHYSICAL REVIEW A
1981; 23 (4): 1673-1678
View details for Web of Science ID A1981LH13600016
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THRESHOLD RESONANCES IN THE ELECTRON PHOTODETACHMENT SPECTRUM OF ACETALDEHYDE ENOLATE ANION - EVIDENCE FOR A LOW-LYING, DIPOLE-SUPPORTED STATE
JOURNAL OF CHEMICAL PHYSICS
1981; 74 (7): 3705-3712
View details for Web of Science ID A1981LK74400008
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INFRARED MULTI-PHOTON INDUCED ELECTRON DETACHMENT FROM SF-6(-)
CHEMICAL PHYSICS LETTERS
1981; 83 (3): 508-511
View details for Web of Science ID A1981MP69900019
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MODELS FOR THE ACTIVE-SITE OF OXYGEN-BINDING HEMOPROTEINS - DIOXYGEN BINDING-PROPERTIES AND THE STRUCTURES OF (2-METHYLIMIDAZOLE)-MESO-TETRA (ALPHA,ALPHA,ALPHA,ALPHA-ORTHO-PIVALAMIDOPHENYL)PORPHYRINATOIRON(II)-ETHANOL AND ITS DIOXYGEN ADDUCT
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1980; 102 (9): 3224-3237
View details for Web of Science ID A1980JP62600055
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SYNTHESIS AND CHARACTERIZATION OF TAILED PICKET FENCE PORPHYRINS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1980; 102 (12): 4182-4192
View details for Web of Science ID A1980JU94200033
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RATES OF PROTON-TRANSFER BETWEEN PYRIDINE BASES IN THE GAS-PHASE - STERIC AND ISOTOPE EFFECTS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1980; 102 (9): 2906-2913
View details for Web of Science ID A1980JP62600007
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ELECTRON PHOTODETACHMENT OF THIOMETHOXYL AND DEUTEROTHIOMETHOXYL ANIONS - ELECTRON-AFFINITIES, VIBRATIONAL FREQUENCIES, AND SPIN-ORBIT-SPLITTING IN CH3S. AND CD3S.
JOURNAL OF CHEMICAL PHYSICS
1980; 72 (1): 694-700
View details for Web of Science ID A1980JB99900095
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INTRINSIC BARRIERS IN NUCLEOPHILIC DISPLACEMENTS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1980; 102 (19): 5993-5999
View details for Web of Science ID A1980KH08800003
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ELECTRON PHOTODETACHMENT FROM MERCAPTYL ANIONS (RS-) - ELECTRON-AFFINITIES OF MERCAPTYL RADICALS AND THE S-H BOND STRENGTH IN MERCAPTANS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1980; 102 (9): 3125-3129
View details for Web of Science ID A1980JP62600040
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SATURATION EFFECTS IN THE FLUENCE DEPENDENCE OF THE INFRARED PHOTO-DISSOCIATION OF CH3OHF-
CHEMICAL PHYSICS LETTERS
1980; 71 (3): 400-404
View details for Web of Science ID A1980JZ34400007
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AN INFRARED MULTI-PHOTON DISSOCIATION STUDY OF RADIATIVE AND COLLISIONAL RELAXATION OF VIBRATIONALLY EXCITED CF3O- IONS
JOURNAL OF CHEMICAL PHYSICS
1980; 73 (12): 6191-6195
View details for Web of Science ID A1980KW25800038
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DIPOLE-SUPPORTED STATES - A VERY LOW-LYING EXCITED-STATE OF ACETALDEHYDE ENOLATE ANION
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1980; 102 (17): 5470-5473
View details for Web of Science ID A1980KD12300007
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ISOTOPE ENRICHMENT AND STEREOCHEMISTRY OF THE PRODUCTS FROM THE REACTION OF ELECTRONICALLY EXCITED IODINE MONOCHLORIDE WITH CIS-1,2-DIBROMOETHYLENE AND TRANS-1,2-DIBROMOETHYLENE
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1979; 101 (24): 7173-7176
View details for Web of Science ID A1979HV43200008
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CARBON-MONOXIDE BINDING TO IRON PORPHYRINS
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
1979; 76 (12): 6035-6039
Abstract
The carbon monoxide affinities of iron complexes of meso-tetra (alpha, alpha, alpha, alpha-o-pivalamidophenyl)porphyrin (the "picket fence" porphyrin) and of a "picket fence" porphyrin derivative with an appended axial base have been measured in solution and compared with the CO affinities of various hemoproteins. The model complexes bind CO with much greater affinity than normal hemoproteins; the role of the steric bulk of distal residues in lowering the CO affinities of the hemoproteins is discussed. The significance of this lowered CO affinity is described with regard to endogenous CO. A discussion of mutant hemoglobins lacking distal residues that sterically inhibit the binding of CO is presented. The use of pressure units versus concentration units in equilibrium expressions is analyzed.
View details for Web of Science ID A1979JA38200004
View details for PubMedID 293699
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RESONANT STATES AT THRESHOLD OBSERVED IN ELECTRON PHOTODETACHMENT CROSS-SECTIONS OF POLYATOMIC NEGATIVE-IONS
JOURNAL OF CHEMICAL PHYSICS
1979; 71 (5): 2088-2094
View details for Web of Science ID A1979HK47800014
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KINETICS AND THERMODYNAMICS OF ION-MOLECULE ASSOCIATION REACTIONS OF WATER, HYDROGEN-SULFIDE, AND BENZENE - COMMENTS ON INTER-MOLECULAR ENTROPY EFFECTS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1979; 101 (9): 2259-2265
View details for Web of Science ID A1979GS92100001
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GAS-PHASE NUCLEOPHILIC DISPLACEMENT-REACTIONS OF NEGATIVE-IONS WITH CARBONYL-COMPOUNDS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1979; 101 (14): 3715-3724
View details for Web of Science ID A1979HB60500002
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PHOTODETACHMENT OF ELECTRONS FROM ANIONS OF HIGH SYMMETRY - ELECTRON PHOTODETACHMENT SPECTRA OF THE CYCLOOCTATETRAENYL AND PERINAPHTHENYL ANIONS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1979; 101 (10): 2567-2570
View details for Web of Science ID A1979GU65900011
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EXPERIMENTAL AND THEORETICAL DETERMINATION OF THE ELECTRON-AFFINITY OF THE ETHYNYL RADICAL, HC2.
JOURNAL OF CHEMICAL PHYSICS
1979; 71 (5): 2057-2061
View details for Web of Science ID A1979HK47800009
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ELECTRON PHOTODETACHMENT FROM CYCLIC ENOLATE ANIONS IN GAS-PHASE - ELECTRON-AFFINITIES OF CYCLIC ENOLATE RADICALS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1978; 100 (15): 4674-4676
View details for Web of Science ID A1978FG72200007
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SYNTHETIC AND MECHANISTIC STUDIES OF REDUCTION OF ALPHA, BETA-UNSATURATED CARBONYL-COMPOUNDS BY BINUCLEAR CLUSTER, NAHFE2(CO)8
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1978; 100 (4): 1119-1140
View details for Web of Science ID A1978EL74800016
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ELECTRON PHOTODETACHMENT FROM ALIPHATIC MOLECULAR ANIONS - GAS-PHASE ELECTRON-AFFINITIES OF METHOXYL, TERT-BUTOXYL, AND NEOPENTOXYL RADICALS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1978; 100 (19): 6142-6148
View details for Web of Science ID A1978FP28200030
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LEWIS ACID-CATALYZED [RFE(CO)4]- ALKYL MIGRATION REACTIONS - MECHANISTIC INVESTIGATION
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1978; 100 (15): 4766-4772
View details for Web of Science ID A1978FG72200022
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ELECTRON PHOTODETACHMENT SPECTROSCOPY OF POLYENE ANIONS - ELECTRON-AFFINITIES OF PENTADIENYL AND HEPTATRIENYL RADICALS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1978; 100 (18): 5595-5597
View details for Web of Science ID A1978FN22000002
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MODEL COMPOUNDS FOR T-STATE OF HEMOGLOBIN
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
1978; 75 (2): 564-568
Abstract
O2 binding to a series of ferrous and cobaltous "picket fence" porphyrins is reported. N-Methylimidazole and covalently attached imidazoles gives O2 binding to ferrous porphyrins with deltaH degrees =-16.2 kcal/mol (-67.7 kJ/mol) and deltaS degrees =-40 eu (standard state, 1 atmosphere O2). Similar studies with cobaltous porphyrins yield deltaH degrees =- 12.8 kcal/mol (-53.5 kJ/mol) and deltaS degrees =- 39 eu. These values match well those of myoglobin and isolated subunits of hemoglobin and their cobalt reconstituted analogues. 1,2-Dimethylimidazole has been successfully used to mimic the presumed restraint of T state hemoglobin. In direct analogy to the decreased cooperativity shown by cobalt-substituted hemoglobin, model cobalt porphyrins show a smaller decrease in O2 affinity than the analogous iron porphyrins when the axial base is hindered. Thermodynamic data are presented. The molecular mechanism of cooperativity in hemoglobin is discussed.
View details for Web of Science ID A1978EQ77900007
View details for PubMedID 273219
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COOPERATIVITY IN O-2 BINDING TO IRON PORPHYRINS
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
1978; 75 (3): 1052-1055
Abstract
The solid-gas O2 binding equilibrium has been studied for for ferrous "picket fence" porphyrinates with sterically hindered axial imidazoles. Such systems show significant cooperativity in their binding of O2: at low O2 pressures a low O2 affinity form exists, and at high O2 pressures a higher O2 affinity form develops. Direct analogies are drawn to the cooperativity shown in O2 binding by hemoglobin. These model systems mimic hemoglobin quantitatively.
View details for Web of Science ID A1978EU94600003
View details for PubMedID 274696
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OXYGEN BINDING TO COBALT PORPHYRINS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1978; 100 (9): 2761-2766
View details for Web of Science ID A1978EW91900031
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INFRARED PHOTODECOMPOSITION OF ETHYL VINYL ETHER - CHEMICAL PROBE OF MULTIPHOTON DYNAMICS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1977; 99 (24): 8063-8064
View details for Web of Science ID A1977EB73900055
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ELECTRON PHOTODETACHMENT FROM NEGATIVE-IONS OF C2V SYMMETRY - ELECTRON-AFFINITIES OF ALLYL AND CYANOMETHYL RADICALS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1977; 99 (11): 3565-3568
View details for Web of Science ID A1977DG50800004
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GAS-PHASE NUCLEOPHILIC DISPLACEMENT-REACTIONS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1977; 99 (13): 4219-4228
View details for Web of Science ID A1977DK39300002
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GAS-PHASE HYDROLYSIS OF PHOSPHORUS ESTERS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1977; 99 (23): 7707-7708
View details for Web of Science ID A1977EA14800050
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PHOTODETACHMENT OF ELECTRONS FROM ENOLATE ANIONS - GAS-PHASE ELECTRON-AFFINITIES OF ENOLATE RADICALS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1977; 99 (22): 7203-7209
View details for Web of Science ID A1977DY69500018
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ANALYSIS OF RATES OF ION-MOLECULE ASSOCIATION REACTIONS - PROTON-BOUND DIMERS OF NH3, CH3NH2, AND (CH3)2NH
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1977; 99 (4): 992-998
View details for Web of Science ID A1977CV65000003
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OXIDATIVE-ADDITION REACTIONS OF NA2FE(CO)4 SUPERNUCLEOPHILE
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1977; 99 (8): 2515-2526
View details for Web of Science ID A1977DB88400019
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PHOTODISSOCIATION OF BUTYROPHENONE CATION - IONIC ANALOGS OF NORRISH TYPE-1 AND TYPE-2 REACTIONS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1977; 99 (6): 1977-1978
View details for Web of Science ID A1977CY72200052
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REACTIONS AND PHOTOCHEMISTRY OF VIBRATIONALLY EXCITED CL-2(-)
CHEMICAL PHYSICS LETTERS
1977; 48 (1): 127-131
View details for Web of Science ID A1977DJ33400031
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CROSS-SECTIONS FOR PHOTODETACHMENT OF ELECTRONS FROM NEGATIVE-IONS NEAR THRESHOLD
JOURNAL OF CHEMICAL PHYSICS
1976; 64 (4): 1368-1375
View details for Web of Science ID A1976BH06300016
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NATURE OF O-2 AND CO BINDING TO METALLOPORPHYRINS AND HEME PROTEINS
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
1976; 73 (10): 3333-3337
Abstract
The O2 vibration of dioxygen adducts of Fe and Co model complexes of alpha,alpha,alpha,alpha-tetrapivalamidophenylporphyrin ("picket fence" porphyrin, TpivPP) with 1-methylimidazole and 1-tritylimidazole as axial bases are reported, obtained with difference techniques between 16O2, 18O2, 169-18O, and NO with a Fourier transform infrared spectrometer. Assignments of upsilono2 are (O2)Fe(TpivPP) 1-methylimidazole, 1159 cm-1 in Nujol; (O2)Fe(TpivPP) 1-tritylimidazole, 1163 in benzene; (O2)Co(TpivPP) 1-methylimidazole, 1150 in Nujol; (O2)Co(TpivPP) 1-tritylimidazole, 1153 in benzene. Comparisons with other known Fe, Co, Cr, and Ti dioxygen complexes are made, and it is concluded that the bent dioxygen ligand is best viewed as bound superoxide, O2-. The CO affinities of various hemoproteins and model systems are discussed. A correlation between the CO stretching frequency and its binding constant is described. The drastically lowered affinity of hemoproteins for CO compared with unencumbered models is attributed to steric hindrance in the distal binding site, which allows discrimination between the already bent FeIII-O2- and the normally linear FeII-CO systems. If the affinity of hemoproteins in living systems for CO relative to O2 were not decreased, then massive poisoning would result from endogenous CO.
View details for Web of Science ID A1976CH08400002
View details for PubMedID 1068445
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DYNAMICS OF PROTON-TRANSFER INVOLVING DELOCALIZED NEGATIVE-IONS IN GAS-PHASE
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1976; 98 (25): 7891-7898
View details for Web of Science ID A1976CN37400001
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ISOMERIZATION OF BICYCLO[2.1.0]PENT-2-ENES
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1976; 98 (18): 5546-5552
View details for Web of Science ID A1976CC22000023
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DEPOLARIZED LIGHT-SCATTERING FROM LIQUIDS
ANNUAL REVIEW OF PHYSICAL CHEMISTRY
1976; 27: 443-463
View details for Web of Science ID A1976CT88400018
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REACTION OF ANTIMONY PENTAFLUORIDE WITH POLY (CARBON MONOFLUORIDE)
MATERIALS RESEARCH BULLETIN
1976; 11 (6): 615-620
View details for Web of Science ID A1976BV09300003
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PHOTODETACHMENT OF ELECTRONS FROM LARGE MOLECULAR SYSTEMS - BENZYL ANION - UPPER LIMIT TO ELECTRON AFFINITY OF C6H5CH2
JOURNAL OF CHEMICAL PHYSICS
1975; 63 (1): 74-76
View details for Web of Science ID A1975AG01900010
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TETRAHEDRAL INTERMEDIATES IN GAS-PHASE IONIC DISPLACEMENT-REACTIONS AT CARBONYL CARBON
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1975; 97 (23): 6685-6688
View details for Web of Science ID A1975AW22500015
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TECHNIQUE FOR DETECTION OF NEUTRAL PRODUCTS IN GAS-PHASE, ION-MOLECULE REACTIONS
INTERNATIONAL JOURNAL OF MASS SPECTROMETRY AND ION PROCESSES
1975; 16 (3): 307-319
View details for Web of Science ID A1975V935200008
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PHOTODETACHMENT OF ELECTRONS FROM TRIFLUOROMETHYL AND TRIFLUOROSILYL IONS - ELECTRON AFFINITIES OF CF-3(.) AND SIF-3(.)
CHEMICAL PHYSICS LETTERS
1975; 30 (1): 17-20
View details for Web of Science ID A1975V268800004
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PHOTODETACHMENT OF ELECTRONS FROM PHENOXIDES AND THIOPHENOXIDE
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1975; 97 (11): 2967-2970
View details for Web of Science ID A1975AD58400008
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PHOTODETACHMENT OF ELECTRONS FROM LARGE MOLECULAR SYSTEMS - PYRROLATE ION - ELECTRON AFFINITY OF C4H4N
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1975; 97 (5): 1160-1162
View details for Web of Science ID A1975V778100033
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DEPOLARIZED RAYLEIGH SPECTROSCOPY STUDIES OF RELAXATION PROCESSES OF POLYSTYRENES IN SOLUTION
MACROMOLECULES
1975; 8 (4): 443-451
View details for Web of Science ID A1975AM36100015
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DEPOLARIZED RAYLEIGH-SCATTERING AND ORIENTATIONAL RELAXATION OF MOLECULES IN SOLUTION .49 MIXTURES OF HEXAFLUOROBENZENE WITH BENZENE AND WITH MESITYLENE
JOURNAL OF CHEMICAL PHYSICS
1975; 63 (1): 53-60
View details for Web of Science ID A1975AG01900007
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CARBON MONOFLUORIDE - EVIDENCE FOR A STRUCTURE CONTAINING AN INFINITE ARRAY OF CYCLOHEXANE BOATS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1974; 96 (25): 7841-7842
View details for Web of Science ID A1974U969200054
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RESONANCE ENERGY OF TRANSITION-STATES - CYCLOBUTENE-BUTADIENE ENERGY SURFACE
ACCOUNTS OF CHEMICAL RESEARCH
1974; 7 (3): 65-71
View details for Web of Science ID A1974S387200001
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ISOTOPE SEPARATION BY SELECTIVE UNIMOLECULAR PHOTOISOMERIZATION
OPTICS COMMUNICATIONS
1974; 12 (2): 223-224
View details for Web of Science ID A1974U544400028
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PHOTODETACHMENT OF NO-(2) - EXPERIMENTAL EVIDENCE FOR A NEW ISOMER
CHEMICAL PHYSICS LETTERS
1974; 25 (3): 318-320
View details for Web of Science ID A1974S800500005
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PHOTODETACHMENT OF ELECTRONS FROM GROUP IVA BINARY HYDRIDE ANIONS - ELECTRON AFFINITIES OF SIH3 AND GEH3 RADICALS
JOURNAL OF CHEMICAL PHYSICS
1974; 61 (11): 4830-4838
View details for Web of Science ID A1974V049600057
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PHOTODETACHMENT OF ELECTRONS FROM ETHYL NITRENE ANION - UPPER LIMIT TO ELECTRON AFFINITY OF C2H5N
CHEMICAL PHYSICS LETTERS
1974; 25 (3): 321-323
View details for Web of Science ID A1974S800500006
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NATURE OF CHROMIUM TRIOXIDE INTERCALATION IN GRAPHITE
CARBON
1974; 12 (2): 199-208
View details for Web of Science ID A1974T147000010
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MOLECULAR-REORIENTATION IN LIQUIDS - EXPERIMENTAL TEST OF HYDRODYNAMIC MODELS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1974; 96 (22): 6840-6843
View details for Web of Science ID A1974U533900004
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WIDE LINE NUCLEAR MAGNETIC-RESONANCE OF F-19 IN GRAPHITE ANTIMONY PENTAFLUORIDE - EVIDENCE FOR RAPID MOTION OF INTERCALATED SPECIES
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS
1974: 924-925
View details for Web of Science ID A1974U720500007
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DEPOLARIZED RAYLEIGH-SCATTERING AND C-13 NMR-STUDIES OF ANISOTROPIC MOLECULAR-REORIENTATION OF AROMATIC-COMPOUNDS IN SOLUTION
JOURNAL OF CHEMICAL PHYSICS
1974; 61 (6): 2255-2261
View details for Web of Science ID A1974U178400013
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GENERALIZED HYDRODYNAMICS AND DEPOLARIZED RAYLEIGH DOUBLET IN ANISALDEHYDE
JOURNAL OF CHEMICAL PHYSICS
1973; 59 (10): 5304-5309
View details for Web of Science ID A1973R768100010
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CHEMISTRY OF DIRADICALS .4. THERMOCHEMISTRY, CALCULATIONS, AND BARRIER TO RING-CLOSURE IN SHORT-CHAIN-LENGTH DIRADICALS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1973; 95 (9): 2849-2852
View details for Web of Science ID A1973P492300018
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PHOTODETACHMENT OF ELECTRONS FROM LARGE MOLECULAR SYSTEMS - CYCLOPENTADIENIDE AND METHYLCYCLOPENTADIENIDE IONS - UPPER LIMIT TO ELECTRON AFFINITIES OF C5H5 AND CH3C5H4
JOURNAL OF CHEMICAL PHYSICS
1973; 59 (9): 5068-5076
View details for Web of Science ID A1973R679800061
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MECHANISM OF ISOMERIZATION OF BICYCLO[2.1.0]PENT-2-ENES
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1973; 95 (15): 5043-5044
View details for Web of Science ID A1973Q249200045
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NATURE OF ALPHA-SULFINYL CARBANION DERIVED FROM METHYL 1-PHENYLETHYL SULFOXIDE
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS
1973: 398-399
View details for Web of Science ID A1973P899100018
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DEPOLARIZED RAYLEIGH-SCATTERING AND ORIENTATIONAL RELAXATION OF MOLECULES IN SOLUTION .2. CHLOROFORM AND NITROBENZENE
JOURNAL OF CHEMICAL PHYSICS
1973; 59 (10): 5310-5320
View details for Web of Science ID A1973R768100011
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HOMOGENEOUS CATALYSIS OF A GAS-PHASE, ION-MOLECULE REACTION
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1973; 95 (3): 927-928
View details for Web of Science ID A1973O745100054
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DEPOLARIZED RAYLEIGH-SCATTERING AND ORIENTATIONAL RELAXATION OF MOLECULES IN SOLUTION .3. CARBOXYLIC-ACIDS
JOURNAL OF CHEMICAL PHYSICS
1973; 59 (10): 5321-5328
View details for Web of Science ID A1973R768100012
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DEPOLARIZED RAYLEIGH-SCATTERING AND ORIENTATIONAL RELAXATION OF MOLECULES IN SOLUTION .1. BENZENE, TOLUENE, AND PARA-XYLENE
JOURNAL OF CHEMICAL PHYSICS
1973; 58 (12): 5570-5578
View details for Web of Science ID A1973Q000900052
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ROLE OF ION PAIRING IN REACTIONS OF METAL-CARBONYL ANIONS .1. CATION-ASSISTED ALKYL-ACYL MIGRATORY INSERTIONS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
1972; 94 (16): 5905-?
View details for Web of Science ID A1972N197300067