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“Green Nanochemistry: Metal Oxide Nanoparticles and Porous Thin Films from Bare Metal Powders” Engelbert Redel, Srebri Petrov, Ömer Dag , Jonathon Moir, Chen Huai, Peter Mirtchev, and Geoffrey A. Ozin, Small, 2011, DOI: 10.1002/smll.201101596
Advocates for green chemistry and nanotechnology have both promised technological solutions to society’s great challenges. Some of the barriers to widespread adoption of nanotechnology have been outlined by Jim Hutchison, and many of these barriers can be addressed by green chemistry. In particular the two issues that the current paper addresses are the excessive waste and the potential hazards associated with the metal precursors.
“Iron-catalyzed Intermolecular [2π-2π] Cycloaddition” Russell, S. K.; Lobkovsky, E.; Chirik, P. J. J. Am. Chem. Soc. 2011, 133, 8858-8861. DOI: 10.1021/ja202992p
As the cost of precious metals increases dramatically along with concerns over the toxicity of 2nd and 3rd row metals, chemists are increasingly turning to employing earth-abundant metals in catalysis, especially iron.
In their recent contribution in the area of base metal catalysis, the Chirik group at Princeton reports an intermolecular, iron-catalyzed cycloaddition reaction. In addition to building on the intramolecular version of the reaction they had previously reported, the current contribution is also notable for their isolation of a catalytically competent intermediate.
The chemistry starts with their remarkable iron bis(dinitrogen) complex 1 (or a related bridging diiron dinitrogen complex), a formally zero-valent compound with an electronic structure better described as a dianionic bis(imino)pyridine ligand bound to an intermediate spin iron(II) ion.
The redox non-innocence of the supporting ligand enables the iron center to do two electron chemistry (required for oxidative addition and reductive elimination), reactions usually reserved for 2nd and 3rd row transition metals. In Chirik’s system, iron generally stays in the preferred ferrous oxidation state, while the ligand undergoes two electron reactions cycling between a neutral donor and a dianionic form during catalysis.
The bond-making and bond-breaking events still occur at the metal center (as for more traditional organometallic reactions, think Pd(0)/Pd(II) chemistry), the trick is that the accompanying redox changes occur at the ligand.
The bis(dinitrogen) complex 1 can catalyze the intermolecular cycloaddition of 1,3-butadiene with ethylene to form vinylcyclobutane. By introducing a methyl group into the butadiene substrate (isoprene), the 1,4 addition product is formed instead.