Page 345 - Arrow Pushing in Inorganic Chemistry A Logical Approach to the Chemistry of the Main Group Elements
P. 345
INDEX 325
discovery, 300–301 phosphorus, 163–6
krypton difluoride, 314–15 alkali-induced disproportionation of, 171–3
O/F ligand exchanges, 303–4 in biology, 163–6
perxenate, 307–8 phosphorylation, 163–6
xenate, 307–8 phosphorus pentoxide, 158–60, 162–3, 271
xenon fluorides, 302–3 phosphorylation, 164
+
as F donors and oxidants, 304–5 pinacol coupling, 54–5, 64–5
Xe–O bonds, 311–12 pink bismuth, 195
nucleophiles, 2–5, 59 pK a values, 9–11
addition to carbon–heteroatom multiple bonds, leaving group and, 9–11
24–6 plumbylenes (Pb), 116
carbon nucleophiles, 3 polystannanes, 113–15
factors contributing to, 5–8 proton transfers (PTs), 15–16
Lewis bases (electron-pair donors), 5 Pummerer rearrangement, 228
nitrogen-based, 3 pyrophosphate linkages, 165
S N 2 paradigm, 2–5
sulfur-based, 3 radical reactions, 35–7
Swain–Scott nucleophilicity, 4–5 heterolysis, 35
homolysis, 35
O/F ligand exchanges, 303–4 initiation step, 36
Olin–Raschig process, 133–4 propagation step, 36
organobismuth chemistry, 195–200 termination step, 36
organoboranes, 70–72, 76 radical trap, 59
organolithium compounds, 58–61 redox potentials, 11
organomagnesium compounds, 58–61 reducing agents
organostannanes, 112–13 group 13-based, 73–6
oxibase scale, 11 s-block metals as, 52–3
oxidation state (OS), 40–41 reductive couplings, 53–6
oxidative additions, 30–32 reductive eliminations, 30–32, 90
oxides, 131–3, 158–60, 215–18 Riley oxidation, 245
oxoacids, 131–3, 215–18, 268–71 Ruppert–Prakash reagent (Me 3 SiCF 3 ), 102–3, 287,
oxoanions, 131–3, 268–71 313
oxohalides, 160–163
ozone, 222–5 S-adenosylmethione (SAM), 169
ozonolysis, 224–5 Sakurai reaction, 108–9
s-block elements, 2, 50–65, See also alkali and
p-block elements, 2 alkaline earth metals
Pauling electronegativities, 6, 7 selenium dihalides, 210–221
pentafluorides (SbF 5 ), 193–5 selenium dioxide, 216, 243–5
perchlorate, 52, 257, 271–4, 288 selenium-mediated oxidations, 243–7
perchloryl fluoride, 274 Shapiro reaction, 144–6
pericyclic reactions, 37 1,2-shift, 32
periodic acid oxidations, 290–291 silanes, 104–6
periodic table, 2 silanols, 99–100
atomic radii, 6–7 -silicon effect, allylsilanes, 106–9
d block, 2 silicones, 100–101
group numbers, 2 silyl anions, 109–12
p block, 2 silyl cations, 122–4
Pauling electronegativities, 6–7 moderately stable silyl cation, 122
s block, 2 silyl protecting groups, 98–103
perxenate, 307–8 silylenes (Si), 46, 97, 116–20
Peterson olefination, 103–4 single bond dissociation energies, 13
Pfitzner–Moffatt oxidation, 227 S N 1 pathways, 20–22
phosphatases, 165 S N 2 paradigm, 2–5
phosphazenes, 180–184 S N 2-Si pathway, 19–20, 96–7, 127
phosphoric anhydride, 164 sodium azide, synthesis of, 135–7
phosphorus ylides, 176–80 sodium thiosulfate, 217–18
