Page 342 - Arrow Pushing in Inorganic Chemistry A Logical Approach to the Chemistry of the Main Group Elements

INDEX
322
6
4
bismuth in organic synthesis, 195–200 -and -sulfuranes, 46
4
pink bismuth, 195 -(methylene)dimethylsulfurane, 46
5
bond dissociation energies (BDEs), 11–14 -(methylene)triphenylphosphorane, 46
single bond dissociation energies, 13 coordination number (CN), 40–41
borazine, 76–8 Corey–Seebach reaction, 231
boron nitride, 78–9 Corey–Winter olefination, 185–6
boryl anion, 87–8 counterions, 64
Bouveault–Blanc reaction, 56 Crown ether, 52
3
-bromanes, 294–8 Cryptand, 52, 56–8, 254, 256–7
bromine pentafluoride, 276 Curtius rearrangement, 149–51
bromine trifluoride, 291–4 cyclooctachalcogen ring formation, 213–15
bromonium ions, 23, 256, 276–7 cyclopolysulfur rings, nucleophilic breakdown of,
Brønsted basicity, 6 211–13
d-block elements, 2
carbonic acid, 98 d-block contraction, 157
carbanions, 26–30
and related synthetic intermediates, 26–30 DBN, 15
carbenes, 29, 115–20 DBU, 15
carbocations, 3–4, 21–2, 32, 38, 122, 128, 173 Dess–Martin periodinane (DMP), 288–90
carbon–carbon multiple bonds, 22–3 diazene, 140–143
electrophilic addition to, 22–3 diazo compounds, 146–9
anti addition, 23 diazonium salts, 138–40
meso compound, 23 dichlorine heptoxide, 271–2
syn addition, 23 Diels-Alder reaction, 37, 52, 199
carbon–heteroatom multiple bonds, nucleophilic diethyl azodicarboxylate (DEAD), 188
addition to, 24–6 diethylaminosulfur trifluoride (DAST), 234
carbon nucleophile, 3 digermyne, 120–121
carbonyl oxide, 224 dihydrogen activation by frustrated lewis pairs (FLPs),
chalcogens, 202–51 61–3
cyclooctachalcogen ring formation, 213–15 diimide, 141–3
cyclopolysulfur rings, nucleophilic breakdown of, dimethyl sulfide (DMS), 203
211–13 dimethyl sulfoxide (DMSO), 226
disulfur dichloride (S Cl 2 ), 209–11 1,3-dipolar additions, 37, 149, 224
2
divalent state, 204–5 dissociative processes, 16–19
higher-valent states, 215–18 dissolving metal reactions, 56–8
higher-valent sulfur fluorides, 234–6 disulfur dichloride (S 2 Cl 2 ), 209–11
higher-valent tellurium, 247–50 divalent state, 204–5
Lawesson’s reagent (LR), 238–9 hydrogen peroxide, 205–9
Martin sulfurane, 236–8 sulfur, 204–5
oxides, 215–18 Döbereiner triad, 203
oxoacids, 215–18
ozone, 222–5 E1 pathways, 20–22
selenium-mediated oxidations, 243–7 electrides, 56
S F 2 , hydrolysis of, 231–4 electrophiles, 2–5
2
sulfur dichloride (SCl 2 ), 209–11 Lewis acids (electron-pair acceptors), 5
sulfur nitrides, 240–243 S N 2 paradigm, 2–5
sulfur oxochlorides, 219–21 electrophilic fluorinating agents, 264–8
sulfur-stabilized carbanions, 228–31 electrophilic reactions
sulfur ylides, 228–31 addition to carbon–carbon multiple bonds, 22–3
Swern and related oxidations, 226–8 addition–elimination, 23–4
Challenger mechanism, 169–71 substitution on aromatics, 23–4
chloramine, 131, 134 electrophilic substitution on aromatics, 23–4
chlorate, 268, 270–273 addition–elimination, 23–4
chlorine dioxide, 269–71 elemental halogens, 254–8
comproportionation, 260 elementary processes, 16–19
convention, 45–6 associative processes, 16–19
5
3
-and -phosphoranes, 46 dissociative processes, 16–19