Crystal structure alkyl hydroperoxides

The largest number of hydrogen bonds in crystal structures of alkyl hydroperoxides refer to intermolecular bonds between the hydroperoxide proton and functionalities of the type 0=X, where X denotes a sulfur (e.g. 27), carbon (e.g. 30) or a phosphorous atom (e.g. 32, Figure 14, Table 7)93,108,115 geometry of [l,2-bis(diphenylphosphinoyl)ethane] bis(2,2-dihydroperoxypropane) (32) in the solid state is a rare example of a bifurcated hydrogen bond between an OOH donor and an 0=X proton acceptor. 

The second largest number of hydrogen bonds in crystal structures of alkyl hydroperoxides refers to interactions of the type OO—H OR R, where R is an alkyl group and R denotes H, alkyl or R O. The OO OR R distances vary between 2.67-2.91 A and the associated O—H O angles range from 152 to 177°. In some compounds, formation of intramolecular hydrogen bonds of the type OO—H 0=X would in principle have been feasible. The number of examples documented in the literature so far is clearly in favor of the intermolecular type of H bonding. 

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... 

Cobalt(III)-alkyl peroxide complexes with the formula Co(BPI)(OOR)(OCOR ) (205 BPI = l,3-bis(2 -pyridylimino)isoindoline R= Bu , CMe2Ph R = Me, Ph, Bu ) have been prepared from the oxidation of Con(BPI)(OCOR ) complexes by alkyl hydroperoxides. The X-ray crystal structure of complex (205) (R=Bu R = Ph) revealed a distorted octahedral environment, with a monodendate OOBuc group and a bidendate carboxylate.635... 

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