Carboxylation of an ansa-Zirconocene Dinitrogen Complex: Regiospecific Hydrazine Synthesis from N2 and CO2
- 8 March 2008
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 130 (13), 4248-4249
- https://doi.org/10.1021/ja8008506
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.Keywords
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