Carboxylation of an ansa-zirconocene dinitrogen complex: regiospecific hydrazine synthesis from N2 and CO2 |
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Authors: | Knobloch Donald J Toomey Hannah E Chirik Paul J |
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Affiliation: | Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853, USA. |
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Abstract: | Addition of 2 equiv of carbon dioxide to the ansa-zirconocene dinitrogen complex resulted in selective insertion into each zirconium nitrogen bond, forming a C2 symmetric dicarboxylated diazenido compound. Treatment with excess Me3SiI furnished the ansa-zirconocene diiodide along with the N,N'-dicarboxylated silylated hydrazine. New nitrogen-carbon bonds were also assembled by addition of methyl triflate. Tri- and tetrasubstituted hydrazines could be formed by treatment with water and Me3SiI, respectively. The regiochemistry of the N2 carboxylation is controlled by the ansa-cyclopentadienyl ligand where the sterically demanding tert-butyl substituents and the C2 symmetry of the dimer dictates the stereochemistry of CO2 insertion. These results demonstrate the ability of zirconium dinitrogen compounds to participate in heterocumulene insertion chemistry. |
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