Hafnocene Puts N2 And CO2 To Work | Chemical & Engineering News
Volume 85 Issue 3 | p. 45 | Concentrates
Issue Date: January 15, 2007

Hafnocene Puts N2 And CO2 To Work

Department: Science & Technology

If chemists could take N2 and CO2 out of the air and convert them into value-added chemicals, they would really have something. Wesley H. Bernskoetter, Emil Lobkovsky, and Paul J. Chirik of Cornell University have opened a door to that possibility by preparing a substituted hydrazine from N2 and CO2 in a reaction mediated by hafnocene, a hafnium bis(cyclopentadienyl) complex (Angew. Chem. Int. Ed., DOI: 10.1002/anie.200604099). Chirik's group has previously shown that hafnocene and zirconocene can preferentially bind N2 side-on (rather than end-on) between two of the metallocene molecules, an orientation that sets up N2 for further reaction (Dalton Trans. 2007, 16). For hafnocene, they now report that reacting the hafnocene-N2 complex with CO2 leads to insertion of CO2 into the Hf-N bonds (shown). Addition of Me3SiI (Me = methyl) liberates the N2-CO2 core by forming the substituted dicarboxyl hydrazine (Me3Si)2N-N(CO2SiMe3)2 mixed with iodinated hafnocene, which can be recycled.

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