Consistent force field calculation of conformations of spiro compounds

Substituent effects on the stabilities of phenoxyl radicals and the acidities of phenoxyl radical cations

“…In other words, this line allows one to eliminate the electronegativity, or other, factor(s) controlling the anion basicity in order to reveal the size of delocalizing, or other, effects on the ABDEs pKHA Figure 2. (a) Points for oxidation potentials of p-phenoxide ions plotted against p/CHA values for p-phenols shown relative to the line for meta substituents derived in Figure 1: 1 (N02), 2 (MeS02), 3 (CN), 4 (CF3), 5 (PhCO), 6 (MeCO), 7 (Br), 8 (Cl), 9 (H), 10 (Ph), 11 (Me), 12 (r-Bu), 13 (MeO), 14 (HO), 15 (Me2N), 16 (NH2), 17 (O'), (b) Points for oxidation potentials of o-phenoxides plotted against p/*HA values of o-phenols shown relative to the line for meta substituents derived in Figure 1: 1 (Cl), 2 (Me), 3 (MeO), 4 (2,6-Me2), 5 (2,6-f-Bu2).…”

Delocalizations in σ-Radical Cations: The Intriguing Structures of Ionized [n]Rotanes

“…Our analysis is based on high-level ab initio and density functional theory (DFT) computations that have become an indispensable tool for studying radical cations derived from simple alkanes , and strained hydrocarbons. ,,− For 1 , the computed and the X-ray structural parameters agree very well; the DFT geometry of 3 matches closely the more recent low-temperature X-ray , crystal structure, as well as lower-level computational data.…”

Perspirocyclopropanated [3]Rotane—A Section of a Carbon Network Containing Spirocyclopropane Units?

“…Analogous to the synthesis of N-nitroso-N-cyclopropylurea,[Z 'I the nitrosourea 11 was obtained from 9 in 39 YO yield. The crucial step-the in situ generation of the diazo [7]triangulane from 11-was achieved with ten equivalents of solid sodium methyl alcoholate at 0°C[221 in a large excess of bicyclopropylidene ( 12).r231 The perspiro- and was isolated in 14% yield.…”