%0 Journal Article %1 Moscherosch.1992 %A Moscherosch, Michael %A Kaim, Wolfgang. %D 1992 %J Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry %K ENDOR ESR ESR;titanium complex dicarbonyl donor;semiquinone electron methyltriisopropoxytitanium;diimine methyltriisopropoxytitanium;ketone methyltriisopropoxytitanium;methyltriisopropoxytitanium prepn radical single stable titanium transfer %N 9 %P 1493--1496 %T EPR/ENDOR detection of stable titanium(III) and titanium(IV) radical products generated by single electron transfer from (iso-PrO)3TiCH3 %X Single-electron-transfer reactions between the stereoselective carbanion source methyltriisopropoxytitanium(IV) as donor and a-diimines, ketones, or a-dicarbonyls as p acceptor substrates exhibit a dichotomy with respect to the ESR-detectable paramagnetic 'escape' products. Substrates with very neg. redn. potentials such as 2,2'-bipyridine yield Ti(III) species, whereas more easily reducible mols. such as dinucleating 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine react to yield ESR-detectable Ti(IV) complexes of the corresponding anion radicals. A very stable paramagnetic product was isolated from the reaction between 3,5-di-tert-butyl-o-quinone (dtbq) and (Me2CHO)3TiMe; this first thermally stable, but apparently configurationally labile, Ti(IV) semiquinone complex [(dtbq-1)Ti(OCHMe2)3].bul. was studied by UV-VIS-NIR absorption and ESR/ENDOR spectroscopy. [on SciFinder(R)]

@article{Moscherosch.1992, abstract = {Single-electron-transfer reactions between the stereoselective carbanion source methyltriisopropoxytitanium(IV) as donor and \textgreek{a}-diimines, ketones, or \textgreek{a}-dicarbonyls as \textgreek{p} acceptor substrates exhibit a dichotomy with respect to the ESR-detectable paramagnetic 'escape' products. Substrates with very neg. redn. potentials such as 2,2'-bipyridine yield Ti(III) species, whereas more easily reducible mols. such as dinucleating 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine react to yield ESR-detectable Ti(IV) complexes of the corresponding anion radicals. A very stable paramagnetic product was isolated from the reaction between 3,5-di-tert-butyl-o-quinone (dtbq) and (Me2CHO)3TiMe; this first thermally stable, but apparently configurationally labile, Ti(IV) semiquinone complex [(dtbq-1)Ti(OCHMe2)3].bul. was studied by UV-VIS-NIR absorption and ESR/ENDOR spectroscopy. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Moscherosch, Michael and Kaim, Wolfgang.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2e60562648ed6280a92f3b4ce06c07f90/huebleriac}, interhash = {5efee7c4ab383bb0c2eea5c54716beb3}, intrahash = {e60562648ed6280a92f3b4ce06c07f90}, issn = {0300-9580}, journal = {Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry}, keywords = {ENDOR ESR ESR;titanium complex dicarbonyl donor;semiquinone electron methyltriisopropoxytitanium;diimine methyltriisopropoxytitanium;ketone methyltriisopropoxytitanium;methyltriisopropoxytitanium prepn radical single stable titanium transfer}, number = 9, pages = {1493--1496}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {EPR/ENDOR detection of stable titanium(III) and titanium(IV) radical products generated by single electron transfer from (iso-PrO)3TiCH3}, year = 1992 }