Solvent effects in the photodenitrogenation of the azoalkane diazabicyclo[2.2.1]hept-2-ene: viscosity- and polarity-controlled stereoselectivity in housane formation from the diazenyl diradical

Literature Information

Publication Date 2002-02-13
DOI 10.1039/B110562K
Impact Factor 3.676
Authors

Waldemar Adam, Manfred Diedering


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Abstract

The stereoselectivity in the liquid-phase photolysis of the diazabicyclo[2.2.1]hept-2-ene (DBH), as expressed in terms of the kinv/kret ratio for the formation of the inverted [2(inv)] versus retained [2(ret)] housanes, depends on the viscosity and bulk polarity of the medium, while hydrogen bonding has little effect on the stereodifferentiation. The similar viscosity profiles of the kinv/kret ratio in alcohols and in isooctane/nujol mixtures manifest the same free-volume requirements and thereby reflect similar frictional impositions on the stereoselective inversion for the DBH photolysis in these solvents. The Onsager bulk-polarity parameter (ε − 1)/(2ε + 1) accounts adequately for the observed solvent influence. This fact implies that stabilization of the dipole moment in the diazenyl diradical 1DZ retards the inversion process during the denitrogenation.

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