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

Journal Article · Wed Apr 11 04:00:00 EDT 1990 · Journal of the American Chemical Society; (USA)

DOI:https://doi.org/10.1021/ja00164a019· OSTI ID:6428894

Balch, A L; Cornman, C R; Olmstead, M M ^[1]

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1. Univ. of California, Davis (USA)

TPPGe(OOCH{sub 2}CH{sub 3}){sub 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){sub 2} and by photolysis of TPPGe(CH{sub 2}CH{sub 3}){sub 2} in the presence of dioxygen. The latter reaction involves successive reactions of the two ethyl groups to give TPPGe(OOCH{sub 2}CH{sub 3})(CH{sub 2}CH{sub 3}) and TPPGe(OOCH{sub 2}CH{sub 3}){sub 2} and the decomposition/hydrolysis products TPPGe(OH)(CH{sub 2}CH{sub 3}) and TPPGe(OH)(OOCH{sub 2}CH{sub 3}). X-ray diffraction studies on both TPPGe(OOCH{sub 2}CH{sub 3}){sub 2} and TPPGe(OCH{sub 2}CH{sub 3}){sub 2} confirm their similar, six-coordinate structures. The ring current shifted {sup 1}H NMR resonances of the axial ligands in these complexes are more effective than electronic spectra in monitoring reaction products. Photolysis of TPPGe(OOCH{sub 2}CH{sub 3}){sub 2} in toluene produces acetaldehyde and ethanol in ratios that are highly temperature dependent.

• OSTI ID: 6428894
• Journal Information: Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 112:8; ISSN 0002-7863; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CARBOXYLIC ACIDS
CHEMICAL REACTIONS
DATA
DATA ANALYSIS
DECOMPOSITION
EXPERIMENTAL DATA
GERMANIUM COMPOUNDS
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
INFORMATION
MEASURING INSTRUMENTS
MEASURING METHODS
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXYGEN COMPOUNDS
PEROXIDES
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
PORPHYRINS
STRUCTURAL CHEMICAL ANALYSIS