sigma.-.pi. Conjugation of carbon-metal bonds. Stereoelectronic and

sigma.-.pi. Conjugation of carbon-metal bonds. Stereoelectronic and inductive effects. Teddy G. Traylor, Walter G. Hanstein, and H. J. Berwin. J. Am...
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reasonable to consider the difference to indicate that neighboring cationic centers by (verti~aI)~',g B-T cononly a fraction of the ester product 2 is attributed to jugation (I) rather than neighboring nucleophilic parradical-pair recombination. Thus together with the ~ ~ , ~c .T ticipation (11). I t has been ~ u g g e s t e d that already established l80 scrambling, intramolecularity Rn of rearrangement in aromatic solvent^,^ and rate6'+, hl determining deprotonation mechanism, l the present findings are compatible with a dual m e ~ h a n i s m ~ins ~ , ~ ~ which the anhydro base 4 cleaves to both radical and I I1 ion pairs. The ester product 2 can result from both but only the radical manifold should give polarization. conjugation, like all other types of T conjugation, requires coplanarity of the C-M bond and the axis of value could be expected among other possible combinations of the two magnetic parameters when a radical pair has accidentally almost equal g the electron-deficient T orbital (or p orbital) as i n values. I n comparison with the carbon radicals which have g values I11 or IV. close to those of the free electrons, the oxygen radicals usually have larger g factors due to larger spin-orbit coupling. The radical pair MI