126294-64-2Relevant academic research and scientific papers
Formation and structure of alkyl peroxide complexes of germanium(IV) porphyrins from direct reactions with alkyl hydroperoxides and by photolysis of alkylgermanium(IV) porphyrins in the presence of dioxygen
Balch, Alan L.,Cornman, Charles R.,Olmstead, Marilyn M.
, p. 2963 - 2969 (2007/10/02)
TPPGe(OOCH2CH3)2 (TPP is the dianion of tetraphenylporphyrin) which has remarkable thermal stability but is hydrolytically sensitive has been prepared by both reaction of ethyl hydroperoxide with TPPGe(OH)2 and by photolysis of TPPGe(CH2CH3)2 in the presence of dioxygen. The latter reaction involves successive reactions of the two ethyl groups to give TPPGe(OOCH2CH3)(CH2CH3) and TPPGe(OOCH2CH3)2 and the decomposition/hydrolysis products TPPGe(O-H)(CH2CH3) and TPPGe(OH)(OOCH2CH3). X-ray diffraction studies on both TPPGe(OOCH2CH3)2 and TPPGe(OCH2CH3)2 confirm their similar, six-coordinate structures. The ring current shifted 1H NMR resonances of the axial ligands in these complexes are more effective than electronic spectra in monitoring reaction products. Photolysis of TPPGe(OOCH2CH3)2 in toluene produces acetaldehyde and ethanol in ratios that are highly temperature dependent. At 23 °C the acetaldehyde/ethanol ratio is 0.55, while at -70 °C it is 3.5.
