32-electron chemistry

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.

An@C28

 

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


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