Alkyl hydroperoxides dihedral angles

The torsion angle R—O—O—H in alkyl hydroperoxides lies in the range of 100 20°, which is comparable to the value for H2O2, either in the gas phase or in the solid state (Tables 1 and 2) . In peroxides of the type R —O—O—(for R, R = alkyl, aryl, vinyl, alkynyl) a progressive increase of the peroxide dihedral angle with the steric demand of R and R is observed (Table 2). 

A survey of crystal structures of 29 compounds (Table 8), in which the alkyl hydroperoxide anions serves as ligand to metal ions, transition metal ions or group 13-17 elements, provides a mean 0—0 bond length of 1.46 0.03 A, an O—O—C angle of 109 2.1° and a M—O—O angle of 112 6.9°. More specialized aspects that deserve to be addressed separately refer to the nature of the M—O bond, the magnitude of the dihedral angle M—O—O—C and the tetrahedral distortion of the peroxide bound C atom. 

Alkyl halides, hydroperoxide synthesis, 327-8 Alkyl hydroperoxides anion ligands, 114-19 covalent radii, 114, 118-19 dihedral angles, 119 geometric parameters, 115-8 tetrahedral distortion, 119 artemisinin formation, 133-4 chlorotriorganosilane reactions, 779-83 crystal structure, 105-14 anomeric effect, 110-11 geometric parameters, 106-9 hydrogen bonding, 103-5, 111-14 tetrahedral distortion, 110 determination, 674... 

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