N,N-dialkylcarbamato mu-oxo derivatives of iron(III)

ABSTRACT A series of homoleptic N,N-dialkylcarbamates of iron(III), Fe(O2CNR2)(3) [R = Et, Pr-i, cyclohexyl (cy), 1-3, respectively] have ken prepared from anhydrous FeCl3 and the amine-CO2 system in toluene. The sparingly soluble N,N-dibenzyl complex of formula Fe(O(2)CNBz(2))(3) (4), was prepared by metathesis from the soluble N,N-di-iso-propyl derivative and NHBz(2)-CO2. When R = Bu-s, the R2NH-CO2 system operating on anhydrous FeCl3 in toluene gave the presumably tetranuclear chloro derivative Fe-4((O2CNBu2)-Bu-s)(11)Cl (5). The nuclearity of this compound was inferred from the crystallographically established structure of the corresponding product of hydrolysis Fe-4(mu(3)-O)((O2CNBu2)-Bu-s)(9)Cl (6), the latter consisting of a rhomb of four iron atoms with axes of 6.28 and 3.37 Angstrom. The mu-oxo derivatives [Fe2O(O2CNEt2)(4)](n) (7), and [Fe2O(O(2)CNcy(2))(4)](n) (8), have been obtained by controlled hydrolysis of the iron(III) homoleptic precursors. The high-nuclearity comp...