Ahh, bismuth. The bastard metal of group 15. Ever an outcast, bismuth grew up in the shadow of his metalloid and nonmetal brethren, forced to adopt their awkward “ine” nomenclature while sitting at the bottom of the totem pole (well…the family doesn’t talk about Ununpentium). What did he do to deserve this? Cursed with a symbol that earned the scorn of the rest of the periodic table, the most sexually liberated of the elements had consigned himself to life beneath the broad umbra of nitrogen and phosphorus.
Then, one day, everything changed. People figured out that bismuth was actually useful! React aryl Grignards with bismuth halides, and the resulting organobismuth compounds could be used for a host of arylation reactions. Bismuth finally had his day in the sun, circa 1989.
Group 15’s Jan Brady may be due for another fifteen minutes of fame, if Alex Gagnon and co-workers have anything to say about it. They’ve managed to synthesize tricyclopropyl bismuthine by reacting cyclopropyl Grignard with bismuth(III) chloride in THF, and they used it to couple cyclopropane to a series of haloaromatics. Iodides worked best, yields were suspiciously low for meta coupling of halophenyl esters and aldehydes, and they found that generating tricyclopropyl bismuthine in situ gave the highest yields. They also tested triethyl bismuthine as a coupling partner, and “gratifyingly” (i.e.–and I can’t take credit for this, someone at UI first said it–they got great results and have no idea why) they observed coupling to ethyl o-bromobenzoate with excellent yield using tetrakis-TPP and potassium carbonate. A report on other alkylbismuthine couplings is coming “in due course.”
Check out the paper here.