| Acknowledgement |
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| Supplementary Material |
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1 | (7) |
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1.1 Stereoelectronic effects -- orbital interactions in control of structure and reactivity |
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1 | (2) |
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1.2 Orbital interactions in theoretical chemistry |
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3 | (1) |
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1.3 The birth of stereoelectronic concepts in organic chemistry |
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4 | (4) |
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6 | (2) |
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2 Direct Effects of Orbital Overlap on Reactivity |
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8 | (34) |
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2.1 Bond formation without bond breaking: types of overlap in two-orbital interactions |
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9 | (16) |
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2.1.1 Factors controlling σ-bond overlap |
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12 | (13) |
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2.2 Bond formation coupled with bond breaking |
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25 | (4) |
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2.2.1 Three-orbital interactions: stereoelectronic reasons for the preferred trajectories of intermolecular attack at a chemical bond |
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25 | (4) |
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2.3 Stereoelectronics of supramolecular interactions |
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29 | (13) |
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2.3.1 FMO interactions in intermolecular complexes |
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29 | (1) |
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2.3.2 Expanding the palette of supramolecular interactions: from H-bonding to Li-, halogen, pnictogen, chalcogen and tetrel binding |
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30 | (6) |
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36 | (6) |
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3 Beyond Orbital Overlap: Additional Factors Important for Orbital Interactions. Classifying Delocalizing Interactions |
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42 | (12) |
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3.1 Electronic count: two-electron, one-electron and three-electron bonds |
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43 | (5) |
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3.2 Isovalent vs. sacrificial conjugation |
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48 | (1) |
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3.3 Neutral, negative, and positive hyperconjugation |
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49 | (5) |
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52 | (2) |
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4 Computational and Theoretical Approaches for Studies of Stereoelectronic Effects |
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54 | (8) |
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4.1 Quantifying orbital interactions |
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54 | (2) |
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4.2 Localized orbitals from delocalized wavefunctions |
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56 | (6) |
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60 | (2) |
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5 General Stereoelectronic Trends -- Donors, Acceptors, and Chameleons |
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62 | (35) |
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5.1 Three types of delocalization:: conjugation, hyperconjugation, and σ-conjugation |
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62 | (1) |
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5.2 Geminal and vicinal interactions |
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63 | (1) |
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5.3 Stereoelectronic main rule: antiperiplanarity |
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64 | (4) |
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5.3.1 Effects of bond polarity |
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65 | (3) |
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5.3.2 Polarity-induced acceptor anisotropy |
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68 | (1) |
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5.4 Scales of donor and acceptor ability of orbitals: polarization, hybridization, and orbital energy effects |
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68 | (23) |
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68 | (13) |
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81 | (3) |
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5.4.3 Stereoelectronic chameleons: donors masquerading as acceptors |
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84 | (7) |
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5.5 Cooperativity of stereoelectronic effects and antiperiplanar lone pair hypothesis (ALPH) theory - several donors working together |
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91 | (1) |
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92 | (5) |
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92 | (5) |
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6 Stereoelectronic Effects with Donor and Acceptor Separated by a Single Bond Bridge: The Broad Spectrum of Orbital Contributions to Conformational Analysis |
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97 | (86) |
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99 | (14) |
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6.1.1 Rotational barrier in ethane |
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99 | (6) |
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6.1.2 Axial/equatorial equilibrium in methylcyclohexane |
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105 | (5) |
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110 | (3) |
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113 | (9) |
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6.2.1 "Eclipsed" and "staggered" conformations of alkenes -- stereoelectronic misnomers |
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114 | (3) |
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117 | (4) |
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121 | (1) |
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122 | (4) |
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6.3.1 Primary, secondary, tertiary carbocation stabilization |
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122 | (2) |
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6.3.2 Hyperconjomers of cyclohexyl cations |
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124 | (1) |
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6.3.3 β-Silicon effect and related β-effects |
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124 | (2) |
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126 | (21) |
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129 | (13) |
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6.4.2 Reverse anomeric effect |
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142 | (1) |
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6.4.3 "Anomeric effects without lone pairs": beyond the n → σ* interactions |
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143 | (4) |
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147 | (20) |
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6.5.1 Esters and related carboxylic acid derivatives |
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147 | (10) |
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6.5.2 Vinyl ethers and enamines |
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157 | (10) |
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167 | (16) |
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6.6.1 Hyperconjugation in alkynes and its relation to the "absence" of conjugation between two triple bonds in 1, 3-diynes |
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168 | (2) |
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170 | (13) |
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7 Stereoelectronic Effects with Donor and Acceptor Separated by a Vinyl Bridge |
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183 | (31) |
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184 | (1) |
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7.1.1 Cis-effect: the case of two o-acceptors |
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184 | (1) |
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7.2 σ/π interactions: allenes vs. alkenes |
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185 | (7) |
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185 | (1) |
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186 | (1) |
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7.2.3 Positive conjugation and hyperconjugation in vinyl systems |
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187 | (1) |
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7.2.4 σ → π* deloclization in allenes: allenyl silanes in reactions with electrophiles |
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188 | (4) |
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7.3 Vinyl halides and their carbanions (transition from σC-H → σ*C-Hal to nc → σ*C-Hal interactions) |
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192 | (4) |
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7.3.1 Heteroatom-containing systems |
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195 | (1) |
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7.4 Diazenes and the isomerization of azo compounds |
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196 | (3) |
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7.5 Antiperiplanarity in coordinated bond-breaking and bond-forming processes: eliminations, fragmentations and additions |
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199 | (8) |
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7.6 Syn-periplanarity: the second best choice |
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207 | (7) |
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208 | (6) |
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8 Remote Stereoelectronic Effects |
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214 | (22) |
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8.1 Extended through space interactions: homoconjugation and homohyperconjugation |
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215 | (8) |
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215 | (2) |
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8.1.2 Homoanomeric effects |
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217 | (6) |
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8.1.3 Cross-hyperconjugation |
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223 | (1) |
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8.2 Double hyperconjugation and through-bond interactions |
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223 | (5) |
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8.3 Combined through-bond and through-space interactions |
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228 | (1) |
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8.4 Symmetry and cooperativity effects in cyclic structures |
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229 | (7) |
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229 | (1) |
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230 | (1) |
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231 | (1) |
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231 | (5) |
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9 Transition State Stabilization with Stereoelectronic Effects: Stereoelectronic Control of Reaction Bottlenecks |
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236 | (21) |
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240 | (3) |
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9.2 Diastereoselection in nucl eophilic addition to carbonyl compounds and other π-systems |
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243 | (2) |
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9.3 Electrophilic addition to enamines |
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245 | (1) |
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9.4 Hyperconjugative assistance to alkyne bending and alkyne cycloadditions |
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246 | (2) |
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9.5 Negative conjugation -- donation from oxygen lone pairs to breaking bonds |
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248 | (3) |
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9.6 Remote lone pairs in radical reactions: fragmentations |
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251 | (6) |
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254 | (3) |
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10 Stereoelectronic Effects in Reaction Design |
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257 | (18) |
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10.1 Static stereoelectronics |
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257 | (2) |
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10.2 Dynamic stereoelectronics |
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259 | (16) |
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273 | (2) |
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11 Stereoelectronic Effects in Action: The Many Doors Opened by Orbital Interactions |
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275 | (47) |
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11.1 Gauche effect (σ → σ* interactions) |
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275 | (8) |
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11.2 Trans-effect -- the cousin of gauche effect in organometallic chemistry |
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283 | (1) |
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11.3 Anomeric effects (n → σ* interactions) |
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284 | (27) |
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11.3.1 Cooperativity and anticooperativity in anomeric systems |
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288 | (1) |
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11.3.2 Spectrum of armed and disarmed glycosides |
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289 | (5) |
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11.3.3 Restoring exo-anomeric effect in carbasugars |
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294 | (17) |
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11.4 Bioorganic chemistry and enzyme reactions |
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311 | (11) |
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316 | (6) |
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12 Probing Stereoelectronic Effects with Spectroscopic Methods |
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322 | (54) |
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12.1 Infrared spectroscopy |
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323 | (12) |
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323 | (8) |
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12.1.2 Red-shifting hydrogen bonds -- an intermolecular version of the Bohlmann effect |
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331 | (4) |
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12.2 Nuclear magnetic resonance spectroscopy |
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335 | (33) |
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12.2.1 Stereoelectronic effects on chemical shifts |
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335 | (1) |
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12.2.2 Diamagnetic effects 1H NMR |
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336 | (2) |
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12.2.3 Paramagnetic effects in 13C NMR |
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338 | (2) |
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12.2.4 Through-space interactions - γ-substituent effects |
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340 | (2) |
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12.2.5 Stereoelectronic effects on coupling constants |
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342 | (26) |
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368 | (8) |
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368 | (8) |
| Index |
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376 | |
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