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The neighboring group effect of fluorine in the tritium labeling of organic substrates with [Cp*(PMe3)IrMe(CH2Cl2)]+[BArf]−, a cationic iridium(III) complex

✍ Scribed by Marc B. Skaddan; Robert G. Bergman


Publisher
John Wiley and Sons
Year
2006
Tongue
French
Weight
159 KB
Volume
49
Category
Article
ISSN
0022-2135

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✦ Synopsis


The cationic Ir(III) complex, [Cp*(PMe 3 )IrMe(CH 2 Cl 2 )][BAr f ] (1, Cpà ¼ Z 5 -C 5 Me 5 , BAr f ¼ MeBðC 6 F 5 Þ 3 ), has been shown to be a useful reagent in the tritium and deuterium labeling of organic substrates. During a recent reaction of 1 with a fluorinated molecule, we observed an unusually high incorporation of tritium ortho to the aromatic fluorines. To probe whether this was an isolated incident or a more general phenomenon, we have investigated the application of 1 towards the tritiation of simple fluorinated organic substrates. Our results indicate that aromatic fluorine indeed does exhibit a neighboring group effect in terms of directing ortho H/T exchange. The directing influence appears to be at least as strong as the hydroxyl moiety reported in previous works.