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.

Academic Appointments


Administrative Appointments


  • Associate Dean of Research, Dean of Research, Stanford University (2005 - Present)
  • Associate Dean for Natural Sciences, Humanities and Sciences, Stanford University (1999 - 2003)
  • Chair, Stanford University Department of Chemistry (1995 - 1996)
  • Chair, Stanford University Department of Chemistry (1979 - 1983)

Honors & Awards


  • National Medal of Science, President of the United States (2002)
  • Award in Chemical Sciences, National Academy of Sciences (2001)
  • Charles Lathrop Parsons Award, American Chemical Society (2017)
  • Willard Gibbs Medal, Chicago Section of the American Chemical Society (2003)
  • Linus Pauling Award, Puget Sound, Oregon and Portland Sections of the American Chemical Society (2002)
  • James Flack Norris Award in Physical Organic Chemistry, American Chemical Society (1986)
  • Award in Pure Chemistry, American Chemical Society (1973)
  • Member, National Academy of Sciences (1976)
  • Member, American Philosophical Society (2004)
  • Fellow, American Chemical Society (2011)
  • D. Sc. Honoris Causa,, The Scripps Research Institute (2009)
  • Honorary Fellow, California Academy of Sciences (1991)
  • Arthur C. Cope Scholar Award, American Chemical Society (1986)
  • R.C. Fuson Award, University of Nevada, Reno (1986)
  • Fellow, American Association for the Advancement of Science (1980)
  • Guggenheim Fellow, John Simon Guggenheim Memorial Foundation (1978)
  • Dean's Award for Distinguished Teaching, Stanford University (1976)
  • Harrison Howe Award, Rochester Section of the American Chemical Society (1976)
  • Member, American Academy of Arts and Sciences (1976)

Boards, Advisory Committees, Professional Organizations


  • Camille and Henry Dreyfus Foundation, Board of Directors (2006 - Present)
  • Committee of Selection, John Simon Guggenheim Memorial Foundation (2004 - 2014)
  • Home Secretary, National Academy of Sciences (2003 - 2011)
  • Chair, Senior Editorial Board, AAAS Science (2001 - 2011)
  • Annual Reviews, Board of Directors (2000 - Present)
  • Board of Trustees, Gordon Research Conferences (1991 - 1995)
  • Member of Council, Gordon Research Conferences (1989 - 1995)
  • Deputy Editor for Physical Sciences, AAAS Science (1985 - 2000)

Professional Education


  • SB, Massachusetts Institute of Technology, Chemistry (1959)
  • PhD, University of California at Berkeley, Chemistry (1963)
  • NSF Postdoctoral Fellow, University of California at Los Angeles, Chemistry (1963)

All Publications


  • Geometry Dependence of the Ring-Opening E2 Reaction in Lactones JOURNAL OF PHYSICAL CHEMISTRY A Chen, X., Walthall, D. A., Brauman, J. I. 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

  • Steric and Solvation Effects in Ionic S(N)2 Reactions JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Chen, X., Regan, C. K., Craig, S. L., Krenske, E. H., Houk, K. N., Jorgensen, W. L., Brauman, J. I. 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

  • Hydrogen Bonding Lowers Intrinsic Nucleophilicity of Solvated Nucleophiles JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Chen, X., Brauman, J. I. 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

  • Chemistry - Not so simple SCIENCE Brauman, J. I. 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

  • Vinyl hydrogen acidities of two stereoisomers JOURNAL OF PHYSICAL CHEMISTRY A Walthall, D. A., Brauman, J. I. 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

  • Kinetics of (porphyrin)manganese(III)-catalyzed olefin epoxidation with a soluble iodosylbenzene derivative EUROPEAN JOURNAL OF ORGANIC CHEMISTRY Collman, J. P., Zeng, L., Wang, H. J., Lei, A., Brauman, J. I. 2006: 2707-2714
  • Enolate structure and electron affinity JOURNAL OF PHYSICAL CHEMISTRY A Walthall, D. A., Karty, J. M., Romer, B., Ursini, O., Brauman, J. I. 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

  • Molecular rotations and dipole-bound state lifetimes JOURNAL OF PHYSICAL CHEMISTRY A Walthall, D. A., Karty, J. M., Brauman, J. I. 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

  • Proton exchange and transesterification reactions of acetate enolates with alcohols in the gas phase JOURNAL OF PHYSICAL CHEMISTRY A Chen, X., Brauman, J. I. 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

  • Acidities in cyclohexanediols enhanced by intramolecular hydrogen bonds JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Chen, X., Walthall, D. A., Brauman, J. I. 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

  • Radical autoxidation and autogenous O-2 evolution in manganese-porphyrin catalyzed alkane oxidations with chlorite INORGANIC CHEMISTRY Slaughter, L. M., Collman, J. P., Eberspacher, T. A., Brauman, J. I. 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

  • Steric retardation of S(N)2 reactions in the gas phase and solution JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Vayner, G., Houk, K. N., JORGENSEN, W. L., Brauman, J. I. 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

  • 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 Collman, J. P., Zeng, L., Brauman, J. I. 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

  • Dynamics of competitive reactions: Endothermic proton transfer and exothermic substitution JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Ren, J. H., Brauman, J. I. 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

  • Determination of the acidity of long chain alcohols using infrared multiple photon dissociation JOURNAL OF PHYSICAL CHEMISTRY A Wong, J., Walthall, D. A., Brauman, J. I. 2002; 106 (51): 12299-12304
  • Conformation-dependent reaction thermochemistry: Study of lactones and lactone enolates in the gas phase JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Karty, J. M., Janaway, G. A., Brauman, J. I. 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

  • Energy deposition in S(N)2 reaction products and kinetic energy effects on reactivity JOURNAL OF PHYSICAL CHEMISTRY A Ren, J. H., Brauman, J. I. 2002; 106 (15): 3804-3813

    View details for DOI 10.1021/jp0141070

    View details for Web of Science ID 000175164400024

  • Steric effects and solvent effects in ionic reactions SCIENCE Regan, C. K., Craig, S. L., Brauman, J. I. 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

  • Mechanism of dihydrogen cleavage by high-valent metal oxo compounds: Experimental and computational studies INORGANIC CHEMISTRY Collman, J. P., Slaughter, L. M., Eberspacher, T. A., Strassner, T., Brauman, J. I. 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

  • The RS-center dot HSR hydrogen bond: Acidities of alpha,omega-dithiols and electron affinities of their monoradicals JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Karty, J. M., Wu, Y. S., Brauman, J. I. 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

  • Multiple active oxidants in cytochrome P-450 model oxidations JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Collman, J. P., Chien, A. S., Eberspacher, T. A., Brauman, J. I. 2000; 122 (45): 11098-11100
  • Energetics and mechanism of alkyl cleavage transition states: Relative gas-phase acidities of alkanes JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Wong, J., Sannes, K. A., Johnson, C. E., Brauman, J. I. 2000; 122 (44): 10878-10885
  • Twist and fluoresce SCIENCE Brauman, J. I. 2000; 290 (5490): 286-287
  • Competitive reaction of axial ligands during biomimetic oxygenations INORGANIC CHEMISTRY Collman, J. P., Chien, A. S., Eberspacher, T. A., Zhong, M., Brauman, J. I. 2000; 39 (20): 4625-4629

    View details for DOI 10.1021/ic000071z

    View details for Web of Science ID 000089707500034

  • Unusual ionic hydrogen bonds: Complexes of acetylides and fluoroform JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Chabinyc, M. L., Brauman, J. I. 2000; 122 (36): 8739-8745

    View details for DOI 10.1021/ja000806z

    View details for Web of Science ID 000089432300020

  • Hydrogen-bonded complexes of methanol and acetylides. Structure and energy correlations JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Chabinyc, M. L., Brauman, J. I. 2000; 122 (22): 5371-5378
  • Direct observation of spin forbidden proton-transfer reactions: (NO-)-N-3+HA ->(HNO)-H-1+A(-) JOURNAL OF PHYSICAL CHEMISTRY A Janaway, G. A., Brauman, J. I. 2000; 104 (9): 1795-1798
  • Negative ion electron photodetachment from a near-blackbody photon source JOURNAL OF PHYSICAL CHEMISTRY A Janaway, G. A., Brauman, J. I. 2000; 104 (6): 1117-1120
  • Translational energy dependence and potential energy surfaces of gas phase S(N)2 and addition-elimination reactions JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Craig, S. L., Zhong, M. L., Brauman, J. I. 1999; 121 (50): 11790-11797
  • A quantitative UV-VIS probe of enantioselectivity in metalloporphyrin catalyzed oxygenation using aluminium model complexes CHEMICAL COMMUNICATIONS Collman, J. P., Wang, Z., Linde, C., Fu, L., Dang, L., Brauman, J. I. 1999: 1783-1784
  • Intramolecular microsolvation of S(N)2 transition states JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Craig, S. L., Brauman, J. I. 1999; 121 (28): 6690-6699
  • Intrinsic structure-reactivity relationships in gas-phase transacylation reactions: Identity exchange of substituted benzoyl chlorides with chloride ion JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Zhong, M. L., Brauman, J. I. 1999; 121 (11): 2508-2515
  • Nonstatistical reactivity in a vibrationally excited S(N)2 intermediate JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Craig, S. L., Zhong, M. L., Brauman, J. I. 1998; 120 (46): 12125-12126
  • Fulvio Cacace: Note of appreciation INTERNATIONAL JOURNAL OF MASS SPECTROMETRY Brauman, J. I. 1998; 180: XIX-XIX
  • Acidity, basicity, and the stability of hydrogen bonds: Complexes of RO-+HCF3 JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Chabinyc, M. L., Brauman, J. I. 1998; 120 (42): 10863-10870
  • alpha-stabilization by silyl and phosphino substitution JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Romer, B., Gatev, G. G., Zhong, M. L., Brauman, J. I. 1998; 120 (12): 2919-2924
  • Gas-phase ionic reactions: Dynamics and mechanism of nucleophilic displacements SCIENCE Chabinyc, M. L., Craig, S. L., Regan, C. K., Brauman, J. I. 1998; 279 (5358): 1882-1886
  • An agostic alternative to the P-450 rebound mechanism JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Collman, J. P., Chien, A. S., Eberspacher, T. A., Brauman, J. I. 1998; 120 (2): 425-426
  • [FHNO](-): An intermediate in a spin-forbidden proton transfer reaction JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Janaway, G. A., Zhong, M. L., Gatev, G. G., Chabinyc, M. L., Brauman, J. I. 1997; 119 (48): 11697-11698
  • Gas-phase ionic reactions of benzyl and methoxide anions JOURNAL OF PHYSICAL ORGANIC CHEMISTRY Gatev, G. G., Zhong, M. L., Brauman, J. I. 1997; 10 (7): 531-536
  • Phase-shifting acceleration of ions in an ion cyclotron resonance spectrometer: Kinetic energy distribution and reaction dynamics JOURNAL OF PHYSICAL CHEMISTRY A Craig, S. L., Brauman, J. I. 1997; 101 (26): 4745-4752
  • Perturbed equilibria and statistical energy redistribution in a gas-phase S(N)2 reaction SCIENCE Craig, S. L., Brauman, J. I. 1997; 276 (5318): 1536-1538
  • Aza-crown-capped porphyrin models of myoglobin: Studies of the steric interactions of gas binding JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Collman, J. P., Herrmann, P. C., Fu, L., Eberspacher, T. A., Eubanks, M., Boitrel, B., Hayoz, P., Zhang, X. M., Brauman, J. I., Day, V. W. 1997; 119 (15): 3481-3489
  • Cyclopentadienyl, indenyl, and fluorenyl anions: Gas-phase and solvation energy contributions to electron detachment energies JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Romer, B., Janaway, G. A., Brauman, J. I. 1997; 119 (9): 2249-2254
  • Unimolecular dynamics in bimolecular ion-molecule reactions BERICHTE DER BUNSEN-GESELLSCHAFT-PHYSICAL CHEMISTRY CHEMICAL PHYSICS Craig, S. L., Brauman, J. I. 1997; 101 (3): 510-515
  • 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 Romer, B. C., Brauman, J. I. 1997; 119 (8): 2054-2055
  • Branching ratios in activated systems JOURNAL OF PHYSICAL CHEMISTRY A Craig, S. L., Zhong, M. L., Choo, B., Brauman, J. I. 1997; 101 (1): 19-24
  • Generation and chemistry of fluorinated acetoxyl and oxyallyl biradical anions (distonic radical anions) in the gas phase JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Zhong, M. L., Chabinyc, M. L., Brauman, J. I. 1996; 118 (49): 12432-12436
  • Electron photodetachment spectroscopy of solvated anions: RO center dot HF- or ROH center dot F-? JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Mihalick, J. E., Gatev, G. G., Brauman, J. I. 1996; 118 (49): 12424-12431
  • Catalytic activation of H-2 and C-H bonds by electron-deficient ruthenium(II) porphyrins INORGANIC CHEMISTRY Collman, J. P., FISH, H. T., Wagenknecht, P. S., TYVOLL, D. A., Chng, L. L., Eberspacher, T. A., Brauman, J. I., Bacon, J. W., PIGNOLET, L. H. 1996; 35 (23): 6746-6754
  • Intramolecular microsolvation of thermoneutral gas-phase S(N)2 reactions JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Craig, S. L., Brauman, J. I. 1996; 118 (28): 6786-6787
  • Alkyl substituent effect in the deprotonation of unsymmetrical ketones JOURNAL OF PHYSICAL CHEMISTRY Johnson, C. E., Sannes, K. A., Brauman, J. I. 1996; 100 (21): 8827-8835
  • Rearrangement and fragmentation mechanisms of vibrationally activated enolate ions in the gas phase JOURNAL OF PHYSICAL CHEMISTRY Sannes, K. A., Brauman, J. I. 1996; 100 (18): 7471-7479
  • Ambident reactivity of enolate anions in the gas phase. Experimental determination of carbon vs oxygen acylation with CF3COCl JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Zhong, M. L., Brauman, J. I. 1996; 118 (3): 636-641
  • Gas-phase nucleophilic displacement reactions JOURNAL OF MASS SPECTROMETRY Olmstead, W. N., Brauman, J. I. 1995; 30 (12): 1653-1662
  • 1,3-HYDROGEN REARRANGEMENTS OF VIBRATIONALLY ACTIVATED ENOLATE IONS IN THE GAS-PHASE JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Sannes, K. A., Brauman, J. I. 1995; 117 (40): 10088-10092
  • ELECTRON-AFFINITIES AND GAS-PHASE ACIDITIES OF ORGANOGERMANIUM AND ORGANOTIN COMPOUNDS JOURNAL OF THE AMERICAN CHEMICAL SOCIETY BRINKMAN, E. A., Salomon, K., Tumas, W., Brauman, J. I. 1995; 117 (17): 4905-4910
  • THROUGH THE GLASS LIGHTLY SCIENCE Weintraub, H., Ashburner, M., Goodfellow, P. N., Lodish, H. F., ARNTZEN, C. J., ANDERSON, P. W., Rice, T. M., Geballe, T. H., Means, A. R., Ranney, H. M., Cech, T. R., COLWELL, R. R., Bourne, H. R., Richter, B., Singer, I. M., Marrack, P., Fearon, D. T., Penzias, A., Bard, A. J., BRINKMAN, W. F., Marks, P. A., VOGELSTEIN, B., KINZLER, K. W., BISHOP, J. M., Zare, R. N., Schatz, G., Benkovic, S. J., Gray, H. B., Valentine, J. S., Crutzen, P. J., Choi, D. W., Nakanishi, S., Kosslyn, S. M., Brauman, J. I., Rees, D. C., BRILL, W. J., SCHELL, J., Luhrmann, R., Will, C. L., Wulf, W., Vermeij, G. J., Arrow, K. J., Smelser, N. J., Anderson, D. L., ABELSON, P. H. 1995; 267 (5204): 1609-1618

    View details for Web of Science ID A1995QM39700026

    View details for PubMedID 7886446

  • THREITOL-STRAPPED MANGANESE PORPHYRINS AS ENANTIOSELECTIVE EPOXIDATION CATALYSTS OF UNFUNCTIONALIZED OLEFINS JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Collman, J. P., Lee, V. J., KELLENYUEN, C. J., Zhang, X. M., Ibers, J. A., Brauman, J. I. 1995; 117 (2): 692-703
  • THE S(N)2 IDENTITY EXCHANGE-REACTION F-+CH3F-]FCH3+F- - DEFINITIVE AB-INITIO PREDICTIONS JOURNAL OF PHYSICAL CHEMISTRY Wladkowski, B. D., Allen, W. D., Brauman, J. I. 1994; 98 (51): 13532-13540
  • 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 Wilbur, J. L., Brauman, J. I. 1994; 116 (20): 9216-9221
  • ALPHA-SILYL-SUBSTITUENT STABILIZATION OF CARBANIONS AND SILYL ANIONS JOURNAL OF THE AMERICAN CHEMICAL SOCIETY BRINKMAN, E. A., Berger, S., Brauman, J. I. 1994; 116 (18): 8304-8310
  • DIOXYGEN BINDING IN IRON AND COBALT PICNIC BASKET PORPHYRINS JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Collman, J. P., Zhang, X. M., Wong, K., Brauman, J. I. 1994; 116 (14): 6245-6251
  • INTERMEDIATES AND POTENTIAL-ENERGY SURFACES IN THERMONEUTRAL CARBONYL ADDITION-ELIMINATION REACTIONS JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Wilbur, J. L., Brauman, J. I. 1994; 116 (13): 5839-5846
  • 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 Wladkowski, B. D., Wilbur, J. L., Brauman, J. I. 1994; 116 (6): 2471-2480
  • BOUND EXCITED ELECTRONIC STATES OF ANIONS JOURNAL OF CHEMICAL PHYSICS BRINKMAN, E. A., Gunther, E., Schafer, O., Brauman, J. I. 1994; 100 (3): 1840-1848
  • THE PROTON-TRANSFER SURFACE OF CH3OHF- JOURNAL OF CHEMICAL PHYSICS Wladkowski, B. D., East, A. L., Mihalick, J. E., Allen, W. D., Brauman, J. I. 1994; 100 (3): 2058-2088
  • APPLICATION OF MARCUS THEORY TO GAS-PHASE SN2 REACTIONS - EXPERIMENTAL SUPPORT OF THE MARCUS THEORY ADDITIVITY POSTULATE JOURNAL OF PHYSICAL CHEMISTRY Wladkowski, B. D., Brauman, J. I. 1993; 97 (50): 13158-13164
  • GAS-PHASE PROTON-TRANSFER AND SUBSTITUTION-REACTIONS - ENERGY-DEPENDENCE AND DISSOCIATION DYNAMICS JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Wilbur, J. L., Wladkowski, B. D., Brauman, J. I. 1993; 115 (23): 10823-10829
  • MOLECULAR ROTATION AND THE OBSERVATION OF DIPOLE-BOUND STATES OF ANIONS JOURNAL OF CHEMICAL PHYSICS BRINKMAN, E. A., Berger, S., Marks, J., Brauman, J. I. 1993; 99 (10): 7586-7594
  • REGIOSELECTIVE AND ENANTIOSELECTIVE EPOXIDATION CATALYZED BY METALLOPORPHYRINS SCIENCE Collman, J. P., Zhang, X. M., Lee, V. J., Uffelman, E. S., Brauman, J. I. 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

  • ASYMMETRIC EPOXIDATION CATALYZED BY AN IRON BINAP CAPPED PORPHYRIN JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS Collman, J. P., Zhang, X. M., Lee, V. J., Brauman, J. I. 1992: 1647-1649
  • THE SN2 IDENTITY EXCHANGE-REACTION CLCH2CN + CL--]CL- + CLCH2CN - EXPERIMENT AND THEORY JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Wladkowski, B. D., Lim, K. F., Allen, W. D., Brauman, J. I. 1992; 114 (23): 9136-9153
  • INFRARED MULTIPLE PHOTON STUDIES OF ALKOXIDE ALCOHOL COMPLEXES JOURNAL OF THE AMERICAN CHEMICAL SOCIETY BAER, S., Brauman, J. I. 1992; 114 (14): 5733-5741
  • ELECTRON PHOTODETACHMENT FROM ORGANOPHOSPHIDE IONS - ELECTRON-AFFINITIES AND SUBSTITUENT EFFECTS IN ORGANOPHOSPHINES AND THEIR CONJUGATE RADICALS JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Berger, S., Brauman, J. I. 1992; 114 (12): 4737-4743
  • KINETIC-MODELS FOR GAS-PHASE ELECTRON-TRANSFER REACTIONS BETWEEN NITROBENZENES JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Han, C. C., Wilbur, J. L., Brauman, J. I. 1992; 114 (3): 887-893
  • SHAPE-SELECTIVE OLEFIN EPOXIDATION CATALYZED BY METALLO PICNIC-BASKET PORPHYRINS ADVANCES IN CHEMISTRY SERIES <D> Collman, J. P., Zhang, X., Lee, V., HEMBRE, R. T., Brauman, J. I. 1992: 153-162
  • 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 Collman, J. P., Zhang, X., Lee, V., HEMBRE, R. T., Brauman, J. I. AMER CHEMICAL SOC. 1992: 153–162
  • ADDITION AND DEPROTONATION IN REACTIONS OF HYDROXIDE ION WITH A BETA-HYDROXYSILANE INTERNATIONAL JOURNAL OF MASS SPECTROMETRY Angelini, G., Johnson, C. E., Brauman, J. I. 1991; 109: 1-14
  • GAS-PHASE PROTON-TRANSFER REACTIONS BETWEEN ALKOXIDE ANIONS JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Dodd, J. A., BAER, S., Moylan, C. R., Brauman, J. I. 1991; 113 (16): 5942-5949
  • REACTION DYNAMICS ON BARRIERLESS REACTION SURFACES - A MODEL FOR ISOERGIC GAS-PHASE PROTON-TRANSFER REACTIONS JOURNAL OF CHEMICAL PHYSICS Lim, K. F., Brauman, J. I. 1991; 94 (11): 7164-7180
  • ROTATIONAL ENHANCEMENT OF THE PROTON-TRANSFER BARRIER FOR ION-MOLECULE REACTIONS ON A DOUBLE-MINIMUM SURFACE CHEMICAL PHYSICS LETTERS Lim, K. F., Brauman, J. I. 1991; 177 (3): 326-330
  • HEMIACETAL ANIONS - A MODEL FOR TETRAHEDRAL REACTION INTERMEDIATES JOURNAL OF THE AMERICAN CHEMICAL SOCIETY BAER, S., BRINKMAN, E. A., Brauman, J. I. 1991; 113 (3): 805-812
  • MECHANISTIC STUDIES OF OLEFIN EPOXIDATION BY A MANGANESE PORPHYRIN AND HYPOCHLORITE - AN ALTERNATIVE EXPLANATION OF SATURATION KINETICS JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Collman, J. P., Brauman, J. I., Hampton, P. D., Tanaka, H., Bohle, D. S., HEMBRE, R. T. 1990; 112 (22): 7980-7984
  • FRAGMENT ISOTOPE DISTRIBUTION AS A SIGNATURE OF MOLECULAR FLUXIONALITY CHEMICAL PHYSICS LETTERS Brauman, J. I., Zare, R. N., Levine, R. D. 1990; 172 (3-4): 231-234
  • DISSOCIATION AND VIBRATION-INDUCED ELECTRON AUTODETACHMENT OF 3-FLUORONITROBENZENE RADICAL-ANION BY INFRARED MULTIPLE PHOTON EXCITATION JOURNAL OF PHYSICAL CHEMISTRY Han, C. C., Brauman, J. I. 1990; 94 (9): 3403-3415
  • ELECTRON-ATTACHMENT CHEMISTRY OF SICL4 - RELEVANCE TO PLASMA REACTIONS INTERNATIONAL JOURNAL OF MASS SPECTROMETRY AND ION PROCESSES Moylan, C. R., Green, S. B., Brauman, J. I. 1990; 96 (3): 299-307
  • 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 Collman, J. P., Hampton, P. D., Brauman, J. I. 1990; 112 (8): 2986-2998
  • 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 Collman, J. P., Hampton, P. D., Brauman, J. I. 1990; 112 (8): 2977-2986
  • ON THE MECHANISTIC DEPENDENCE OF THE AFFINITY DECAY JOURNAL OF CHEMICAL PHYSICS Hjelmfelt, A., Brauman, J. I., Ross, J. 1990; 92 (6): 3569-3578
  • GAS-PHASE PROTON-TRANSFER FROM TOLUENES TO BENZYL ANIONS JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Han, C. C., Brauman, J. I. 1989; 111 (17): 6491-6496
  • GAS-PHASE ACIDITIES OF ORGANOSILANES AND ELECTRON-AFFINITIES OF ORGANOSILYL RADICALS JOURNAL OF THE AMERICAN CHEMICAL SOCIETY WETZEL, D. M., Salomon, K. E., Berger, S., Brauman, J. I. 1989; 111 (11): 3835-3841
  • VIBRATIONALLY INDUCED ELECTRON DETACHMENT - A RATE FOR ELECTRON LOSS FROM VIBRATIONALLY EXCITED ACETONE ENOLATE ANION JOURNAL OF PHYSICAL CHEMISTRY FOSTER, R. F., Tumas, W., Brauman, J. I. 1989; 93 (1): 61-68
  • ROTATIONAL STRUCTURE IN AN EXCITED VIBRONIC BAND OF THE DIPOLE-SUPPORTED STATE OF CYANOMETHYL ANION, CH2CN- JOURNAL OF CHEMICAL PHYSICS WETZEL, D. M., Brauman, J. I. 1989; 90 (1): 68-73
  • QUANTITATIVE MEASURE OF ALPHA-SILYL CARBANION STABILIZATION - THE ELECTRON-AFFINITY OF (TRIMETHYLSILYL)METHYL RADICAL JOURNAL OF THE AMERICAN CHEMICAL SOCIETY WETZEL, D. M., Brauman, J. I. 1988; 110 (25): 8333-8336
  • INFRARED MULTIPLE-PHOTON DECOMPOSITION OF [CH3OHF]- AND C6H5CH2- JOURNAL OF PHYSICAL CHEMISTRY Salomon, K. E., Brauman, J. I. 1988; 92 (24): 6948-6953
  • ADVANCES IN INSTRUMENTATION SCIENCE Brauman, J. I. 1988; 242 (4876): 165-165

    View details for Web of Science ID A1988Q436800001

    View details for PubMedID 17787639

  • CARBON AND PROTON BASICITY JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Brauman, J. I., Han, C. C. 1988; 110 (17): 5611-5613
  • ELECTRON-TRANSFER COMPETES WITH PROTON-TRANSFER IN GAS-PHASE ACID-BASE REACTIONS JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Han, C. C., Brauman, J. I. 1988; 110 (12): 4048-4049
  • SPECTROSCOPY AND DYNAMICS OF THE DIPOLE-SUPPORTED STATE OF ACETYL FLUORIDE ENOLATE ANION JOURNAL OF CHEMICAL PHYSICS Marks, J., Brauman, J. I., Mead, R. D., Lykke, K. R., Lineberger, W. C. 1988; 88 (11): 6785-6792
  • REVERSIBLE BINDING OF DINITROGEN AND DIOXYGEN BY A RUTHENIUM PICNIC-BASKET PORPHYRIN JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Collman, J. P., Brauman, J. I., Fitzgerald, J. P., SPARAPANY, J. W., Ibers, J. A. 1988; 110 (11): 3486-3495
  • SYNTHESIS, CHARACTERIZATION, AND X-RAY STRUCTURE OF THE RUTHENIUM PICNIC-BASKET PORPHYRINS JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Collman, J. P., Brauman, J. I., Fitzgerald, J. P., Hampton, P. D., Naruta, Y., SPARAPANY, J. W., Ibers, J. A. 1988; 110 (11): 3477-3486
  • MECHANISTIC STUDIES OF GAS-PHASE NEGATIVE-ION UNIMOLECULAR DECOMPOSITIONS - ALKOXIDE ANIONS JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Tumas, W., FOSTER, R. F., Brauman, J. I. 1988; 110 (9): 2714-2722
  • FRONTIERS IN CHEMISTRY SCIENCE Brauman, J. I. 1988; 240 (4851): 373-373

    View details for Web of Science ID A1988N019200001

    View details for PubMedID 17784056

  • MANGANESE PICNIC BASKET PORPHYRINS - CYTOCHROME-P-450 ACTIVE-SITE ANALOGS BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN Collman, J. P., Brauman, J. I., Fitzgerald, J. P., Hampton, P. D., Naruta, Y., Michida, T. 1988; 61 (1): 47-57
  • AN INVESTIGATION OF THE MECHANISM OF NON-PHOTOCHEMICAL HOLE BURNING OF RESORUFIN IN ETHANOL GLASS CHEMICAL PHYSICS LETTERS Kokai, F., Tanaka, H., Brauman, J. I., Fayer, M. D. 1988; 143 (1): 1-5
  • EFFECT OF HYDROGEN-BOND STRENGTH ON RESORUFIN NONPHOTOCHEMICAL HOLE BURNING IN ETHANOL-2,2,2-TRIFLUOROETHANOL GLASSES CHEMICAL PHYSICS LETTERS Tanaka, H., Kokai, F., Brauman, J. I., Fayer, M. D. 1987; 142 (5): 371-375
  • PHOTODISSOCIATION SPECTROSCOPY OF THE NEGATIVE-ION DIMER OF TOLUQUINONE JOURNAL OF THE AMERICAN CHEMICAL SOCIETY COMITA, P. B., Brauman, J. I. 1987; 109 (25): 7591-7597
  • CAPACITANCE BRIDGE DETECTOR AND SIGNAL LOCK FOR ION-CYCLOTRON RESONANCE SPECTROMETRY REVIEW OF SCIENTIFIC INSTRUMENTS Marks, J., Drzaic, P. S., FOSTER, R. F., WETZEL, D. M., Brauman, J. I., UPPAL, J. S., Staley, R. H. 1987; 58 (8): 1460-1463
  • ELECTRON PHOTODETACHMENT SPECTROSCOPY OF TRAPPED NEGATIVE-IONS CHEMICAL REVIEWS WETZEL, D. M., Brauman, J. I. 1987; 87 (3): 607-622
  • SPECTROSCOPY OF REACTIVE INTERMEDIATES - ELECTRON PHOTODETACHMENT FROM SOLVATED ANIONS JOURNAL OF CHEMICAL PHYSICS Moylan, C. R., Dodd, J. A., Han, C. C., Brauman, J. I. 1987; 86 (10): 5350-5357
  • PHOTOCHEMISTRY OF AQUEOUS PERMANGANATE ION JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Lee, D. G., Moylan, C. R., Hayashi, T., Brauman, J. I. 1987; 109 (10): 3003-3010
  • MATERIALS SCIENCE SCIENCE Brauman, J. I. 1987; 235 (4792): 953-953

    View details for Web of Science ID A1987G168200001

    View details for PubMedID 17782221

  • A STEPWISE MECHANISM FOR GAS-PHASE UNIMOLECULAR ION DECOMPOSITIONS - ISOTOPE EFFECTS IN THE FRAGMENTATION OF TERT-BUTOXIDE ANION JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Tumas, W., FOSTER, R. F., Pellerite, M. J., Brauman, J. I. 1987; 109 (4): 961-970
  • INVOLVEMENT OF CYANIDE IN THE REGULATION OF ETHYLENE BIOSYNTHESIS PLANT PHYSIOLOGY AND BIOCHEMISTRY Pirrung, M. C., Brauman, J. I. 1987; 25 (1): 55-61
  • INTRINSIC NUCLEOPHILICITY ADVANCES IN CHEMISTRY SERIES Brauman, J. I., Dodd, J. A., Han, C. C. 1987: 23-33
  • MARCUS THEORY APPLIED TO REACTIONS WITH DOUBLE-MINIMUM POTENTIAL SURFACES JOURNAL OF PHYSICAL CHEMISTRY Dodd, J. A., Brauman, J. I. 1986; 90 (16): 3559-3562
  • 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 Marks, J., WETZEL, D. M., COMITA, P. B., Brauman, J. I. 1986; 84 (10): 5284-5289
  • DIMETHYLSILANONE ENOLATE ANION - COMPETITIVE FRAGMENTATION AND ELECTRON AUTODETACHMENT OF VIBRATIONALLY EXCITED SILOXIDE ANIONS IN THE GAS-PHASE JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Tumas, W., Salomon, K. E., Brauman, J. I. 1986; 108 (10): 2541-2546
  • OXYGENATION OF STYRENE BY CYTOCHROME-P-450 MODEL SYSTEM - A MECHANISTIC STUDY JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Collman, J. P., Kodadek, T., Brauman, J. I. 1986; 108 (10): 2588-2594
  • 2-PULSE 2-LASER PHOTODISSOCIATIONS OF MOLECULAR-IONS - COLLISIONAL RELAXATION OF BROMO-3-(TRIFLUOROMETHYL)-BENZENE CATION JOURNAL OF CHEMICAL PHYSICS Barfknecht, A. T., Brauman, J. I. 1986; 84 (7): 3870-3881
  • COMPETING CHANNELS IN INFRARED MULTIPLE PHOTON DECOMPOSITION INTERNATIONAL JOURNAL OF CHEMICAL KINETICS Moylan, C. R., Brauman, J. I. 1986; 18 (3): 379-398
  • COMPUTERS SCIENCE Brauman, J. I. 1986; 231 (4741): 905-905

    View details for Web of Science ID A1986A067700001

    View details for PubMedID 17740277

  • REACTIONS OF A RHODIUM(I) MACROCYCLE WITH ORGANIC DIHALIDES - OXIDATIVE-ADDITION AND BETA-ELIMINATION PATHWAYS ORGANOMETALLICS Collman, J. P., Brauman, J. I., Madonik, A. M. 1986; 5 (2): 218-222
  • RHODIUM(III)-TO-RHODIUM(I) ALKYL TRANSFER - A RHODIUM MACROCYCLE WHICH IS BOTH NUCLEOPHILE AND LEAVING GROUP ORGANOMETALLICS Collman, J. P., Brauman, J. I., Madonik, A. M. 1986; 5 (2): 215-218
  • OXIDATIVE ADDITION MECHANISMS OF A 4-COORDINATE RHODIUM(I) MACROCYCLE ORGANOMETALLICS Collman, J. P., Brauman, J. I., Madonik, A. M. 1986; 5 (2): 310-322
  • STRUCTURE AND REACTIVITY IN IONIC REACTIONS JOURNAL OF PHYSICAL CHEMISTRY Han, C. C., Dodd, J. A., Brauman, J. I. 1986; 90 (3): 471-477
  • 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 Collman, J. P., Brauman, J. I., Meunier, B., Hayashi, T., Kodadek, T., Raybuck, S. A. 1985; 107 (7): 2000-2005
  • MECHANISTIC INFORMATION FROM INFRARED MULTIPLE PHOTON DECOMPOSITION - THE ETHYLISOPROPYLAMINE PROTON-TRANSFER SYSTEM JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Moylan, C. R., Brauman, J. I. 1985; 107 (4): 761-765
  • EXPERIMENTAL AND THEORETICAL INVESTIGATION OF THE AZIDE ANION (N-3-) IN THE GAS-PHASE BERICHTE DER BUNSEN-GESELLSCHAFT-PHYSICAL CHEMISTRY CHEMICAL PHYSICS Illenberger, E., COMITA, P. B., Brauman, J. I., FENZLAFF, H. P., Heni, M., Heinrich, N., Koch, W., Frenking, G. 1985; 89 (10): 1026-1031
  • GAS-PHASE ION CHEMISTRY SCIENCE COMITA, P. B., Brauman, J. I. 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

  • PRODUCT BRANCHING IN INFRARED MULTIPLE PHOTON DECOMPOSITION OF GAS-PHASE IONS - MECHANISTIC IMPLICATIONS FOR PROTON-TRANSFER REACTIONS JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Moylan, C. R., JASINSKI, J. M., Brauman, J. I. 1985; 107 (7): 1934-1940
  • ELECTRON PHOTODETACHMENT SPECTROSCOPY OF SOLVATED ANIONS - A PROBE OF STRUCTURE AND ENERGETICS CHEMICAL PHYSICS LETTERS Moylan, C. R., Dodd, J. A., Brauman, J. I. 1985; 118 (1): 38-39
  • ELECTRON PHOTODETACHMENT FROM PHENYLNITRENE, ANILIDE, AND BENZYL ANIONS - ELECTRON-AFFINITIES OF THE ANILINO AND BENZYL RADICALS AND PHENYLNITRENE JOURNAL OF PHYSICAL CHEMISTRY Drzaic, P. S., Brauman, J. I. 1984; 88 (22): 5285-5290
  • 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 Collman, J. P., Brauman, J. I., Meunier, B., Raybuck, S. A., Kodadek, T. 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

  • A DETERMINATION OF THE TRIPLET SINGLET SPLITTING IN PHENYLNITRENE VIA PHOTODETACHMENT SPECTROSCOPY JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Drzaic, P. S., Brauman, J. I. 1984; 106 (12): 3443-3446
  • SPECTROSCOPY AND DYNAMICS OF THE DIPOLE-BOUND STATE OF ACETALDEHYDE ENOLATE JOURNAL OF CHEMICAL PHYSICS Mead, R. D., Lykke, K. R., Lineberger, W. C., Marks, J., Brauman, J. I. 1984; 81 (11): 4883-4892
  • ENTROPY BOTTLENECKS IN ION MOLECULE REACTIONS JOURNAL OF CHEMICAL PHYSICS Dodd, J. A., GOLDEN, D. M., Brauman, J. I. 1984; 80 (5): 1894-1899
  • INFRARED MULTIPLE PHOTON PHOTOCHEMISTRY OF GAS-PHASE IONS ISRAEL JOURNAL OF CHEMISTRY Tumas, W., FOSTER, R. F., Brauman, J. I. 1984; 24 (3): 223-231
  • DYNAMICS AND REACTION-MECHANISMS OF ORGANIC IONS IN THE GAS-PHASE PURE AND APPLIED CHEMISTRY Barfknecht, A. T., Dodd, J. A., Salomon, K. E., Tumas, W., Brauman, J. I. 1984; 56 (12): 1809-1818
  • O-2 AND CO BINDING TO IRON(II) PORPHYRINS - A COMPARISON OF THE PICKET FENCE AND POCKET PORPHYRINS JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Collman, J. P., Brauman, J. I., Iverson, B. L., Sessler, J. L., Morris, R. M., Gibson, Q. H. 1983; 105 (10): 3052-3064
  • GAS-PHASE ACID-BASE CHEMISTRY ANNUAL REVIEW OF PHYSICAL CHEMISTRY Moylan, C. R., Brauman, J. I. 1983; 34: 187-215
  • INTRINSIC BARRIERS IN NUCLEOPHILIC DISPLACEMENTS - A GENERAL-MODEL FOR INTRINSIC NUCLEOPHILICITY TOWARD METHYL CENTERS JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Pellerite, M. J., Brauman, J. I. 1983; 105 (9): 2672-2680
  • MECHANISTIC ASPECTS OF A HOMOGENEOUS CARBON-MONOXIDE HYDROGENATION CATALYST-IR4(CO)12 IN MOLTEN ALCL3-NACL JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Collman, J. P., Brauman, J. I., Tustin, G., WANN, G. S. 1983; 105 (12): 3913-3922
  • A SILICA-SUPPORTED RHODIUM HYDROFORMYLATION CATALYST - EVIDENCE FOR DINUCLEAR ELIMINATION JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Collman, J. P., Belmont, J. A., Brauman, J. I. 1983; 105 (25): 7288-7294
  • MULTIPLE DECOMPOSITION PATHWAYS IN INFRARED MULTIPLE-PHOTON-INDUCED REACTIONS OF IONS CHEMICAL PHYSICS LETTERS Moylan, C. R., JASINSKI, J. M., Brauman, J. I. 1983; 98 (1): 1-5
  • SYNTHESIS AND CHARACTERIZATION OF THE POCKET PORPHYRINS JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Collman, J. P., Brauman, J. I., Collins, T. J., Iverson, B. L., Lang, G., Pettman, R. B., Sessler, J. L., Walters, M. A. 1983; 105 (10): 3038-3052
  • EFFECT OF AXIAL BASE ON DIOXYGEN AND CARBON-MONOXIDE AFFINITIES OF IRON(II) PORPHYRINS - IMIDAZOLE VS PYRIDINE INORGANIC CHEMISTRY Collman, J. P., Brauman, J. I., Doxsee, K. M., Sessler, J. L., Morris, R. M., Gibson, Q. H. 1983; 22 (10): 1427-1432
  • INFRARED MULTI-PHOTON PHOTODETACHMENT OF NEGATIVE-IONS IN THE GAS-PHASE JOURNAL OF THE AMERICAN CHEMICAL SOCIETY MEYER, F. K., JASINSKI, J. M., Rosenfeld, R. N., Brauman, J. I. 1982; 104 (3): 663-667
  • 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 JASINSKI, J. M., Rosenfeld, R. N., MEYER, F. K., Brauman, J. I. 1982; 104 (3): 652-658
  • NUCLEOPHILIC-SUBSTITUTION ACS SYMPOSIUM SERIES Pellerite, M. J., Brauman, J. I. 1982; 198: 81-102
  • PHOTO-DISSOCIATION OF STILBENE RADICAL CATION JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Gooden, R., Brauman, J. I. 1982; 104 (6): 1483-1486
  • INFRARED MULTI-PHOTON DISSOCIATION OF THE METHANOL SOLVATE OF THE FLUORIDE-ION, CH3OHF- JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Rosenfeld, R. N., JASINSKI, J. M., Brauman, J. I. 1982; 104 (3): 658-663
  • ELECTRON PHOTODETACHMENT STUDY OF SULFUR-HEXAFLUORIDE ANION - COMMENTS ON THE STRUCTURE OF SF6- JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Drzaic, P. S., Brauman, J. I. 1982; 104 (1): 13-19
  • PROTON-TRANSFER REACTIONS BETWEEN 9-ALKYLFLUORENE AND (9-ALKYLFLUORENYL)LITHIUM IN ETHER JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Murdoch, J. R., Bryson, J. A., McMillen, D. F., Brauman, J. I. 1982; 104 (2): 600-610
  • RATES OF PROTON ABSTRACTION FROM CONJUGATED DIENES IN THE GAS-PHASE HELVETICA CHIMICA ACTA MEYER, F. K., Pellerite, M. J., Brauman, J. I. 1981; 64 (4): 1058-1062
  • PHOTODETACHMENT OF THE AZIDE ANION IN THE GAS-PHASE - ELECTRON-AFFINITY OF THE AZIDE RADICAL JOURNAL OF THE AMERICAN CHEMICAL SOCIETY JACKSON, R. L., Pellerite, M. J., Brauman, J. I. 1981; 103 (7): 1802-1805
  • ELECTRON PHOTODETACHMENT FROM HS- - THE ELECTRON-AFFINITY OF HS PHYSICAL REVIEW A JANOUSEK, B. K., Brauman, J. I. 1981; 23 (4): 1673-1678
  • THRESHOLD RESONANCES IN THE ELECTRON PHOTODETACHMENT SPECTRUM OF ACETALDEHYDE ENOLATE ANION - EVIDENCE FOR A LOW-LYING, DIPOLE-SUPPORTED STATE JOURNAL OF CHEMICAL PHYSICS JACKSON, R. L., HIBERTY, P. C., Brauman, J. I. 1981; 74 (7): 3705-3712
  • INFRARED MULTI-PHOTON INDUCED ELECTRON DETACHMENT FROM SF-6(-) CHEMICAL PHYSICS LETTERS Drzaic, P. S., Brauman, J. I. 1981; 83 (3): 508-511
  • AN INFRARED MULTI-PHOTON DISSOCIATION STUDY OF RADIATIVE AND COLLISIONAL RELAXATION OF VIBRATIONALLY EXCITED CF3O- IONS JOURNAL OF CHEMICAL PHYSICS JASINSKI, J. M., Brauman, J. I. 1980; 73 (12): 6191-6195
  • SYNTHESIS AND CHARACTERIZATION OF TAILED PICKET FENCE PORPHYRINS JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Collman, J. P., Brauman, J. I., Doxsee, K. M., HALBERT, T. R., BUNNENBERG, E., LINDER, R. E., LAMAR, G. N., Delgaudio, J., Lang, G., Spartalian, K. 1980; 102 (12): 4182-4192
  • RATES OF PROTON-TRANSFER BETWEEN PYRIDINE BASES IN THE GAS-PHASE - STERIC AND ISOTOPE EFFECTS JOURNAL OF THE AMERICAN CHEMICAL SOCIETY JASINSKI, J. M., Brauman, J. I. 1980; 102 (9): 2906-2913
  • ELECTRON PHOTODETACHMENT OF THIOMETHOXYL AND DEUTEROTHIOMETHOXYL ANIONS - ELECTRON-AFFINITIES, VIBRATIONAL FREQUENCIES, AND SPIN-ORBIT-SPLITTING IN CH3S. AND CD3S. JOURNAL OF CHEMICAL PHYSICS JANOUSEK, B. K., Brauman, J. I. 1980; 72 (1): 694-700
  • 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 Jameson, G. B., MOLINARO, F. S., Ibers, J. A., Collman, J. P., Brauman, J. I., Rose, E., Suslick, K. S. 1980; 102 (9): 3224-3237
  • INTRINSIC BARRIERS IN NUCLEOPHILIC DISPLACEMENTS JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Pellerite, M. J., Brauman, J. I. 1980; 102 (19): 5993-5999
  • DIPOLE-SUPPORTED STATES - A VERY LOW-LYING EXCITED-STATE OF ACETALDEHYDE ENOLATE ANION JOURNAL OF THE AMERICAN CHEMICAL SOCIETY WETMORE, R. W., Schaefer, H. F., HIBERTY, P. C., Brauman, J. I. 1980; 102 (17): 5470-5473
  • 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 JANOUSEK, B. K., Reed, K. J., Brauman, J. I. 1980; 102 (9): 3125-3129
  • SATURATION EFFECTS IN THE FLUENCE DEPENDENCE OF THE INFRARED PHOTO-DISSOCIATION OF CH3OHF- CHEMICAL PHYSICS LETTERS Rosenfeld, R. N., JASINSKI, J. M., Brauman, J. I. 1980; 71 (3): 400-404
  • EXPERIMENTAL AND THEORETICAL DETERMINATION OF THE ELECTRON-AFFINITY OF THE ETHYNYL RADICAL, HC2. JOURNAL OF CHEMICAL PHYSICS JANOUSEK, B. K., Brauman, J. I., SIMONS, J. 1979; 71 (5): 2057-2061
  • CARBON-MONOXIDE BINDING TO IRON PORPHYRINS PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA Collman, J. P., Brauman, J. I., Doxsee, K. M. 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

  • RESONANT STATES AT THRESHOLD OBSERVED IN ELECTRON PHOTODETACHMENT CROSS-SECTIONS OF POLYATOMIC NEGATIVE-IONS JOURNAL OF CHEMICAL PHYSICS JACKSON, R. L., Zimmerman, A. H., Brauman, J. I. 1979; 71 (5): 2088-2094
  • 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 JASINSKI, J. M., Rosenfeld, R. N., GOLDEN, D. M., Brauman, J. I. 1979; 101 (9): 2259-2265
  • GAS-PHASE NUCLEOPHILIC DISPLACEMENT-REACTIONS OF NEGATIVE-IONS WITH CARBONYL-COMPOUNDS JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Asubiojo, O. I., Brauman, J. I. 1979; 101 (14): 3715-3724
  • 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 Datta, S., Brauman, J. I., Zare, R. N. 1979; 101 (24): 7173-7176
  • PHOTODETACHMENT OF ELECTRONS FROM ANIONS OF HIGH SYMMETRY - ELECTRON PHOTODETACHMENT SPECTRA OF THE CYCLOOCTATETRAENYL AND PERINAPHTHENYL ANIONS JOURNAL OF THE AMERICAN CHEMICAL SOCIETY GYGAX, R., MCPETERS, H. L., Brauman, J. I. 1979; 101 (10): 2567-2570
  • ELECTRON PHOTODETACHMENT FROM CYCLIC ENOLATE ANIONS IN GAS-PHASE - ELECTRON-AFFINITIES OF CYCLIC ENOLATE RADICALS JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Zimmerman, A. H., JACKSON, R. L., JANOUSEK, B. K., Brauman, J. I. 1978; 100 (15): 4674-4676
  • MODEL COMPOUNDS FOR T-STATE OF HEMOGLOBIN PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA Collman, J. P., Brauman, J. I., Doxsee, K. M., HALBERT, T. R., Suslick, K. S. 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

  • COOPERATIVITY IN O-2 BINDING TO IRON PORPHYRINS PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA Collman, J. P., Brauman, J. I., Rose, E., Suslick, K. S. 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

  • SYNTHETIC AND MECHANISTIC STUDIES OF REDUCTION OF ALPHA, BETA-UNSATURATED CARBONYL-COMPOUNDS BY BINUCLEAR CLUSTER, NAHFE2(CO)8 JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Collman, J. P., Finke, R. G., Matlock, P. L., Wahren, R., KOMOTO, R. G., Brauman, J. I. 1978; 100 (4): 1119-1140
  • ELECTRON PHOTODETACHMENT FROM ALIPHATIC MOLECULAR ANIONS - GAS-PHASE ELECTRON-AFFINITIES OF METHOXYL, TERT-BUTOXYL, AND NEOPENTOXYL RADICALS JOURNAL OF THE AMERICAN CHEMICAL SOCIETY JANOUSEK, B. K., Zimmerman, A. H., Reed, K. J., Brauman, J. I. 1978; 100 (19): 6142-6148
  • LEWIS ACID-CATALYZED [RFE(CO)4]- ALKYL MIGRATION REACTIONS - MECHANISTIC INVESTIGATION JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Collman, J. P., Finke, R. G., Cawse, J. N., Brauman, J. I. 1978; 100 (15): 4766-4772
  • ELECTRON PHOTODETACHMENT SPECTROSCOPY OF POLYENE ANIONS - ELECTRON-AFFINITIES OF PENTADIENYL AND HEPTATRIENYL RADICALS JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Zimmerman, A. H., GYGAX, R., Brauman, J. I. 1978; 100 (18): 5595-5597
  • OXYGEN BINDING TO COBALT PORPHYRINS JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Collman, J. P., Brauman, J. I., Doxsee, K. M., HALBERT, T. R., Hayes, S. E., Suslick, K. S. 1978; 100 (9): 2761-2766
  • PHOTODISSOCIATION OF BUTYROPHENONE CATION - IONIC ANALOGS OF NORRISH TYPE-1 AND TYPE-2 REACTIONS JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Gooden, R., Brauman, J. I. 1977; 99 (6): 1977-1978
  • ANALYSIS OF RATES OF ION-MOLECULE ASSOCIATION REACTIONS - PROTON-BOUND DIMERS OF NH3, CH3NH2, AND (CH3)2NH JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Olmstead, W. N., LEVON, M., GOLDEN, D. M., Brauman, J. I. 1977; 99 (4): 992-998
  • ELECTRON PHOTODETACHMENT FROM NEGATIVE-IONS OF C2V SYMMETRY - ELECTRON-AFFINITIES OF ALLYL AND CYANOMETHYL RADICALS JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Zimmerman, A. H., Brauman, J. I. 1977; 99 (11): 3565-3568
  • PHOTODETACHMENT OF ELECTRONS FROM ENOLATE ANIONS - GAS-PHASE ELECTRON-AFFINITIES OF ENOLATE RADICALS JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Zimmerman, A. H., Reed, K. J., Brauman, J. I. 1977; 99 (22): 7203-7209
  • OXIDATIVE-ADDITION REACTIONS OF NA2FE(CO)4 SUPERNUCLEOPHILE JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Collman, J. P., Finke, R. G., Cawse, J. N., Brauman, J. I. 1977; 99 (8): 2515-2526
  • REACTIONS AND PHOTOCHEMISTRY OF VIBRATIONALLY EXCITED CL-2(-) CHEMICAL PHYSICS LETTERS Asubiojo, O. I., MCPETERS, H. L., Olmstead, W. N., Brauman, J. I. 1977; 48 (1): 127-131
  • GAS-PHASE NUCLEOPHILIC DISPLACEMENT-REACTIONS JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Olmstead, W. N., Brauman, J. I. 1977; 99 (13): 4219-4228
  • INFRARED PHOTODECOMPOSITION OF ETHYL VINYL ETHER - CHEMICAL PROBE OF MULTIPHOTON DYNAMICS JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Rosenfeld, R. N., Brauman, J. I., Barker, J. R., GOLDEN, D. M. 1977; 99 (24): 8063-8064
  • GAS-PHASE HYDROLYSIS OF PHOSPHORUS ESTERS JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Asubiojo, O. I., Brauman, J. I., Levin, R. H. 1977; 99 (23): 7707-7708
  • REACTION OF ANTIMONY PENTAFLUORIDE WITH POLY (CARBON MONOFLUORIDE) MATERIALS RESEARCH BULLETIN Ebert, L. B., Huggins, R. A., Brauman, J. I. 1976; 11 (6): 615-620
  • 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 Collman, J. P., Brauman, J. I., HALBERT, T. R., Suslick, K. S. 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

  • DEPOLARIZED LIGHT-SCATTERING FROM LIQUIDS ANNUAL REVIEW OF PHYSICAL CHEMISTRY Bauer, D. R., Brauman, J. I., Pecora, R. 1976; 27: 443-463
  • DYNAMICS OF PROTON-TRANSFER INVOLVING DELOCALIZED NEGATIVE-IONS IN GAS-PHASE JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Farneth, W. E., Brauman, J. I. 1976; 98 (25): 7891-7898
  • CROSS-SECTIONS FOR PHOTODETACHMENT OF ELECTRONS FROM NEGATIVE-IONS NEAR THRESHOLD JOURNAL OF CHEMICAL PHYSICS Reed, K. J., Zimmerman, A. H., ANDERSEN, H. C., Brauman, J. I. 1976; 64 (4): 1368-1375
  • ISOMERIZATION OF BICYCLO[2.1.0]PENT-2-ENES JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Farneth, W. E., Damore, M. B., Brauman, J. I. 1976; 98 (18): 5546-5552
  • PHOTODETACHMENT OF ELECTRONS FROM LARGE MOLECULAR SYSTEMS - BENZYL ANION - UPPER LIMIT TO ELECTRON AFFINITY OF C6H5CH2 JOURNAL OF CHEMICAL PHYSICS Richardson, J. H., Stephenson, L. M., Brauman, J. I. 1975; 63 (1): 74-76
  • TETRAHEDRAL INTERMEDIATES IN GAS-PHASE IONIC DISPLACEMENT-REACTIONS AT CARBONYL CARBON JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Asubiojo, O. I., BLAIR, L. K., Brauman, J. I. 1975; 97 (23): 6685-6688
  • DEPOLARIZED RAYLEIGH SPECTROSCOPY STUDIES OF RELAXATION PROCESSES OF POLYSTYRENES IN SOLUTION MACROMOLECULES Bauer, D. R., Brauman, J. I., Pecora, R. 1975; 8 (4): 443-451
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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 Bauer, D. R., Brauman, J. I., Pecora, R. 1975; 63 (1): 53-60
  • PHOTODETACHMENT OF ELECTRONS FROM TRIFLUOROMETHYL AND TRIFLUOROSILYL IONS - ELECTRON AFFINITIES OF CF-3(.) AND SIF-3(.) CHEMICAL PHYSICS LETTERS Richardson, J. H., Stephenson, L. M., Brauman, J. I. 1975; 30 (1): 17-20
  • PHOTODETACHMENT OF ELECTRONS FROM PHENOXIDES AND THIOPHENOXIDE JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Richardson, J. H., Stephenson, L. M., Brauman, J. I. 1975; 97 (11): 2967-2970
  • PHOTODETACHMENT OF ELECTRONS FROM LARGE MOLECULAR SYSTEMS - PYRROLATE ION - ELECTRON AFFINITY OF C4H4N JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Richardson, J. H., Stephenson, L. M., Brauman, J. I. 1975; 97 (5): 1160-1162
  • CARBON MONOFLUORIDE - EVIDENCE FOR A STRUCTURE CONTAINING AN INFINITE ARRAY OF CYCLOHEXANE BOATS JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Ebert, L. B., Brauman, J. I., Huggins, R. A. 1974; 96 (25): 7841-7842
  • RESONANCE ENERGY OF TRANSITION-STATES - CYCLOBUTENE-BUTADIENE ENERGY SURFACE ACCOUNTS OF CHEMICAL RESEARCH Stephens, L. M., Brauman, J. I. 1974; 7 (3): 65-71
  • DEPOLARIZED RAYLEIGH-SCATTERING AND C-13 NMR-STUDIES OF ANISOTROPIC MOLECULAR-REORIENTATION OF AROMATIC-COMPOUNDS IN SOLUTION JOURNAL OF CHEMICAL PHYSICS Bauer, D. R., Alms, G. R., Brauman, J. I., Pecora, R. 1974; 61 (6): 2255-2261
  • MOLECULAR-REORIENTATION IN LIQUIDS - EXPERIMENTAL TEST OF HYDRODYNAMIC MODELS JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Bauer, D. R., Brauman, J. I., Pecora, R. 1974; 96 (22): 6840-6843
  • ISOTOPE SEPARATION BY SELECTIVE UNIMOLECULAR PHOTOISOMERIZATION OPTICS COMMUNICATIONS Brauman, J. I., OLEARY, T. J., Schawlow, A. L. 1974; 12 (2): 223-224
  • PHOTODETACHMENT OF NO-(2) - EXPERIMENTAL EVIDENCE FOR A NEW ISOMER CHEMICAL PHYSICS LETTERS Richards, J. H., Stephens, L. M., Brauman, J. I. 1974; 25 (3): 318-320
  • PHOTODETACHMENT OF ELECTRONS FROM GROUP IVA BINARY HYDRIDE ANIONS - ELECTRON AFFINITIES OF SIH3 AND GEH3 RADICALS JOURNAL OF CHEMICAL PHYSICS Reed, K. J., Brauman, J. I. 1974; 61 (11): 4830-4838
  • PHOTODETACHMENT OF ELECTRONS FROM ETHYL NITRENE ANION - UPPER LIMIT TO ELECTRON AFFINITY OF C2H5N CHEMICAL PHYSICS LETTERS Richards, J. H., Stephens, L. M., Brauman, J. I. 1974; 25 (3): 321-323
  • NATURE OF CHROMIUM TRIOXIDE INTERCALATION IN GRAPHITE CARBON Ebert, L. B., Huggins, R. A., Brauman, J. I. 1974; 12 (2): 199-208
  • 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 Ebert, L. B., Huggins, R. A., Brauman, J. I. 1974: 924-925
  • HOMOGENEOUS CATALYSIS OF A GAS-PHASE, ION-MOLECULE REACTION JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Brauman, J. I., LIEDER, C. A., White, M. J. 1973; 95 (3): 927-928
  • DEPOLARIZED RAYLEIGH-SCATTERING AND ORIENTATIONAL RELAXATION OF MOLECULES IN SOLUTION .1. BENZENE, TOLUENE, AND PARA-XYLENE JOURNAL OF CHEMICAL PHYSICS Alms, G. R., Bauer, D. R., Brauman, J. I., Pecora, R. 1973; 58 (12): 5570-5578
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  • MECHANISM OF ISOMERIZATION OF BICYCLO[2.1.0]PENT-2-ENES JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Brauman, J. I., Farneth, W. E., Damore, M. B. 1973; 95 (15): 5043-5044
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  • NATURE OF ALPHA-SULFINYL CARBANION DERIVED FROM METHYL 1-PHENYLETHYL SULFOXIDE JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS Damore, M. B., Brauman, J. I. 1973: 398-399
  • DEPOLARIZED RAYLEIGH-SCATTERING AND ORIENTATIONAL RELAXATION OF MOLECULES IN SOLUTION .2. CHLOROFORM AND NITROBENZENE JOURNAL OF CHEMICAL PHYSICS Alms, G. R., Bauer, D. R., Brauman, J. I., Pecora, R. 1973; 59 (10): 5310-5320
  • GENERALIZED HYDRODYNAMICS AND DEPOLARIZED RAYLEIGH DOUBLET IN ANISALDEHYDE JOURNAL OF CHEMICAL PHYSICS Alms, G. R., Bauer, D. R., Brauman, J. I., Pecora, R. 1973; 59 (10): 5304-5309
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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 Collman, J. P., Cawse, J. N., Brauman, J. I. 1972; 94 (16): 5905-?