Subject Index
The Foundations of Physical Organic Chemistry: Fifty Years of the James Flack Norris Award Downloaded from pubs.acs.org by 46.148.115.96 on 12/02/18. For personal use only.
D Diradicals cyclobutane-1,2,3,4-tetraone, (CO)4, 294 diradicals, future research, 297 three diradicals, CH2 groups, 298f diradicals, history, 254 chemistry professor, 256 Chichibabin’s (1) hydrocarbons, 254f Diels-Alder trapping, generation and stereospecific, 254f triplet TMM, generation, 255f ΔEST, measurements in diradicals, 277 (CO)5•−, NIPE spectrum, 281f negative ion photoelectron spectroscopy (NIPES), 278 NIPES experiment, schematic depiction, 279f non-zero overlaps, vibrational wave functions, 282f vibrational progressions, 280 ΔEST, size, 276 ground state of a diradical, prediction, 272 Ovchinnikov’s equation, 275 square CBD and tetramethyleneethane (TME), NBMOs, 274f TMM and meta-benzoquinodimethane (MBQDM), NBMOs, 273f Hund’s rule in diradicals, violations, 290 cyclooctatetraene (COT), geometry, 293 1,2,4,5-tetramethylenebenzene (TMB), starred and unstarred carbons, 292f introduction D4h transition structure (TS), 253f diradicals/biradicals, 251 singlet-triplet energy differences, experimental techniques, 252 PPP calculations on diradicals, results, 257 dynamic spin polarization, schematic depiction, 268f Hund’s rule, 264 lowest singlet and triplet states, 265 lowest singlet state of TMM, geometry, 269 low-lying electronic states, 262 NBMOs, 270f planar allene, nonbonding (NB)MOs, 264f
planar allene, violation of Hund’s rule, 266 planar singlet TMM, wave functions, 271 relative PPP energies, schematic depiction, 263f singlet TMM versus singlet CBD, 270 singlet wave function, 261 TMM and CBD, PPP calculations, 259 trimethylenemethane, singlet and triplet states, 268 triplet state, schematic depiction, 267f two components, schematic depiction, 260f radical anions, NIPE spectra, 283 bonding, schematic depiction, 286f Lineberger’s experimental values, 287 MBQ•−, NIPE spectra, 289f MBQDM, NIPE spectrum, 285f MBQDM, schematic depiction, 284f planar TMM, three electronic states, 284f possible resonance contributors, 288f simulated vibrational structure, NIPE spectrum, 296f two MOs, 295f Doering, William von Eggers, 199 Doering, Bill, 200f bullvalene story, 213 Chinese graduate program (CGP), 219 departmental seminars, 207 deuterium-exchange fellowship, 215 diazomethane, 214 diazomethane, quantities, 201 dihalocarbene addition, stereochemistry, 208 dissertation, 209 Doering's nickname, 212 NMU/KOH reaction, 216 nuclear non-proliferation, 220 organic chemistry, 205 organic chemistry, laboratory technique, 213 quantitative analysis, 202 reaction mechanismwise, 218 spiropentane, carbon-carbon bonds, 205 Stanford chemists, 210 weekly group seminars, 210 wet chemistry, 201 young Doering, Bill, 204f
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F Free radical physical organic chemistry, 223 CKI and KUI at 12 years of age, 227f CKI and KUI at 70 years of age, 227f CKI skiing, 224f electron paramagnetic resonance, 235 garden in Sussex, 225f great water-ski caper, 224f hydrocarbon oxidation, absolute rate constants, 230 hydrocarbon oxidation by phenols, mechanism of inhibition, 228 2,6-di-tertbutyl-4-methylphenol, 229 KUI skiing, 225f nanosecond laser flash photolysis (LFP) and solvent effects, 245 1998 NSERC medal, 249f christened sequential proton loss electron transfer, 248s hydrogen bond acceptor (HBA) solvent, 246 quantitative explanation, 247 NOCT, invention of a nitric oxide cheleotropic, 244 Norris Award, 226 peroxyl radical trapping antioxidants, 238 physical organic chemistry, competitive kinetic methods, 241 α-tocopherol, bioactivity, 239s α-tocopherol, chemical significance, 238c α-tocopherol, sold as vitamin E, 240 persistent carbon-centered radicals, 234 pro-oxidant, vitamin E, 242 quantum mechanical tunneling, 236 reduction of alkyl halides, absolute rate constants, 231 synthesis via a chain reaction, advantage, 233 SOTS-1, invention of the first superoxide thermal source, 243
H Hydrogen isotopes, 77 deuterium, discovery, 78 hydrogen-deuterium asymmetry, 79 1-bromobutane-1-d, racemization, 83f chlorosulfite, SN2 reaction, 84f
early optically active deuterium compounds, 80f iodine isotopes, SN2 exchange, 82f optically active 1-butanol-1-d, preparation, 81f smaller methyl, favored transition structure, 81f secondary α-deuterium isotope effects, 84 cycloaddition of nitrostyrene to cyclopentadiene, isotope effects, 89f cycloaddition reactions, synchronicity, 88f out-of-plane bending motions, 86f solvolysis, α-d isotope effects, 88f some bending vibrations, 85f vibration frequency, effect, 87f tritium, 89
N Norbornyl cation isomers, 139 conclusions, 166 historical background, 142 camphenyl cation, representation, 143f 2-norbornyl cation, 144t norbornyl compounds vs. cyclohexyl, solvolysis rates, 145f infrared spectroscopy, classical vs. nonclassical structure, 153 Born-Oppenheimer molecular dynamics (BOMD) simulation, 158f C7H11+, experimental spectrum, 155f C7H11+ from protonation of norbornene, experimental spectrum, 156f clarifying wagner-meerwein reaction products, 161f 1,3-dimethylcyclopentenyl, computed spectra, 157f Duncan’s IR-PD apparatus, 154f 2-endo-norbornyl cation, 158 endo-2-norbornyl cation, norpinyl product, 160f excerpts from Friedrich and Winstein, 164f exo vs. endo 2-norbornyl solvolyses, 159f L2-endo-norbornyl (norpinyl) cations, 165f low energy isomers, 156f
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pinene-HCl to bornyl chloride (endo) rearrangement, 162f pinyl to 2-endo-norbornyl dyotropic rearrangement, 163f potential experiment solution, 153f puzzling wagner-meerwein product stereochemistry, 161f introduction, 140 Schleyer, Paul von R., 140f 2-norbornyl cation, direct observation, 146 excerpts from Roberts, Lee, 149f excerpts from Saunders, Schleyer, 148f excerpts from Schleyer, Watts, 147f 2-norbornyl cation, 150f 2-norbornyl cation, 1H NMR spectra, 149f overview, 141 norbornyl cation citations, 142f norbornyl citations, 141f symmetrical bridged structure, classical ions, 145 exo vs. endo 2-norbornyl solvolyses, 146f nonclassical ion vs. rapid equilibrium model, 145f X-ray crystallography, adventures, 150 [C7H11]+[Al2Br7]- • CH2Br2 crystal structure, asymmetric unit, 152f The Nonclassical Ion Problem, cover, 152f 2-norbornyl cation, disorder, 151f unsubstituted 2-norbornyl cation XRD structure, 153f Norris, James Flack brief biography, 3 Dr. Norris, James Flack, 4f leadership qualities, 5 National Research Council Section, 6 Norris's right eye, cataract surgery, 7 dedication, 18 James Flack Norris awards, 16 physical organic chemistry, early days, 1 quantitative organic chemistry, contributions, 12 chemical theory, early differences, 13 Columbia University, presentation, 14 ethanolysis, rates, 15t Remsen, Ira, influence, 8 selenium, tellurium and molecular addition compounds, early scientific research, 9 tricoordinate carbon, 10
O Optical activity, study computational studies, 25 gas phase measurements, 36 cavity ring-down polarimeter, 37f optical rotation and solvent dielectric constant, relationship, 38f introduction, 23 minimal basis sets, use, 35 logarithmic scale, effect of basis set, 36f norbornenone, 40 optical activity, 26 Rosenfeld’s equation, 27 optical activity, experimental studies, 28 calculated conformational energies, 29f calculated optical rotations, relationship, 31f 3-chloro-2-butene, calculated optical rotation profile, 30f 3-Chloro-1-butene conformers, 29f conformational mixtures, calculated and observed specific rotations, 32t oxidation, mechanisms, 25 small ring compounds, 24 spectroscopic studies, 26 sum-over states calculations, 38 chloropropionitrile, sum-over-states study for 1500 excited states, 39f chloropropionitrile, sum-over-states study for first 125 excited states, 39f norbornenone model and its C=C-C-C torsion angle, relationship, 40f twisted achiral compounds, 32 B3LYP calculated specific rotations, effect of basis set, 33t difference density plot, 34f twisted butane, calculated optical rotations, 32f
P Physical organic chemistry antiaromaticity, 62 increasing antiaromatic cyclobutadiene character, 64f parent antiaromatic compounds, 64f symmetric cations, triplet ground states, 65f aromatic and antiaromatic molecules, electrical conductivity, 66 aromaticity, 62
313
departmental seminars, 112 graduate school, 104 graduate student Havill, Martha, 101f granddaughter Kylie, 110f MS in nuclear chemistry, UC-Berkeley, 105 Ph.D, 114 Russell and Martha, married on June 6, 1953, 100 Russell family, 106 Russell symposium, 109f skiing trip, 116 successful academic researcher, 117 Sun Valley, 107f Trahanovsky, Walter, 113 wedding day, 102f Russell’s research, 118 semidione story, 124 acyloin, oxidation, 125f anion radicals, 126f ESR spectra, 127f p-benzoquinone, one electron reduction, 125f proton splitting, 129f semidiones, early synthetic methods, 128f
cyclopropenyl cation and cyclopropenone, 63f biomimetic chemistry and enzyme mimics, 67 catalysis by polymers, 69 combat cancer, mechanism, 72 suberoylanilide hydroxamic acid, 73f enzyme mimics, cyclodextrins, 68 enzyme mimics, reaction of steroids, 67 formose reaction and prebiotic chemistry, 70 importance, 61 my studies, 62 physical organic chemistry, future, 73 selective stereochemistry, creation, 71 some enzyme reactions, mechanisms, 70 thiamine pyrophosphate, mechanism of catalysis, 66 thiazolium zwitterions, 66f transition state geometries, 69
R Russell, Glen A. carbanions, oxidation, 123 Russell’s suggested chain reaction, 124s electron transfer, 130 unsaturated systems, electron transfer, 131f exploration, 133 introduction, 93 DPPH, resonance structures, 95f Koelsch’s radical, resonance structures, 96f Russell, Glen, Iowa State faculty member, 94f triphenyl methyl radical, resonance structures, 95f Iowa State, early work, 121 NBS story, 122 organic synthesis, research, 132 Purdue, early research, 119 Russell mechanism, 120f Russell’s life and career, 97 1993 Gordon conference, 108f 1963 nobel prizes, 115 academic gowns, Russell, 99f age 6 photo, 98f associate professor, 103 career, overview, 111 chemistry department parking lot, 110f dance skills, Russell, 107f
S Schleyer, Paul from adamantane to dodecahedrane, 175 Diels-Alder product, 177s research facilities, Princeton, 176 sulphuric acid treatment, 175s applied spectroscopy and hydrogen bonding, 185 carbocation rearrangement mechanisms, 178 computational chemist, beginnings, 191 early years, 170 epilogue, 195 Schleyer, Paul and Streitwieser, Andrew, 195f graduate student, 172 interminable norbornyl controversy, 189 introduction, 169 Schleyer, Paul, Erlangen, 170f move to Erlangen, 180 quantum chemistry, Pople, John, 192 solvolysis reactions, 187 undergraduate years, Princeton, 171 Solvation, thermochemical studies physical organic chemistry, beginnings, 49
314
complete thermodynamic analysis, problem 1, 53 preparation of o-di-t-butyl benzene, schematic, 58f synthesis and strain energy, project 4, 57 t-butyl chloride solvolysis, problem 3, 55
Arnett group, typical solution calorimeter, 53f organic chemistry, solvation, 51 organic reactions, elucidation, 50 solution calorimeters, 52 solution calorimetry, application adduct, presumed structure, 57f alkyl halide solvolysis, problem 2, 54 aqueous-ethanol solvents, mole fraction water, 56f
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