32-electron chemistry
by mitch on Dec 07 2008 (3156 Views)We all remember learning about octets and valence electrons in school. We may also remember the first time we saw an 18-electron transition metal complex. This week Dognon et al. discuss the possibility of 32-electron organometallic complexes.[JACS] In order to reach 32-electrons, f-orbital participation is essential. Below is a picture of a hypothetical organometallic complex with 28 carbons in a cage around an actinide element.
Although these systems are not new, as the Smalley group made U@C28 in the gas-phase in '92,[Science] Dognon et al. examine a series of these systems for different actinides. The major conclusion is that the plutonium system is theoretically predicted to have the largest bonding energy for its Pu4+@C28 complex. Since fullerenes and the intercalation of metals often only need heat to be synthesized, I wouldn't be surprised if these complexes have already been made but missed as impurities and byproducts.
Link to paper: A Predicted Organometallic Series Following a 32-Electron Principle: An@C28 (An = Th, Pa+, U2+, Pu4+)
Update 1: Jyllian Kemsley also covered it at C&EN -- Stable Caged Actinides Proposed(subscription)
Mitch
Anybody ever hear of the band They Might Be Giants?
http://en.wikipedia.org/wiki/They_Might_Be_Giants
Anyway, they have a old song called 32 foot steps.
Replace "foot steps" with electrons!
Fan made video with the song:
http://www.youtube.com/watch?v=wW9qXw483_0
Yes I am a odd person.