Abstract
The synthesis, structures, and reactivity of dinuclear Fe0 complexes of N-heterocyclic carbenes (NHCs, denoted as L) are reported. The NHC adducts of ferric chloride (L)FeCl3 were prepared from the reactions of FeCl3 with L in toluene. The reduction of (L)FeCl3 with KC8 resulted in the formation of the dinuclear Fe0 complexes Fe2{μ-η1(C):η6(arene)-L}2 (2a, L = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (IMes); 2b, L = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr)), in which NHC ligands bridge two iron atoms using one of the arene rings as an η6 ligand. Their magnetic properties are different: 2a is paramagnetic and 2b is diamagnetic. The dinuclear complexes 2a,b serve as precursors for monomeric (NHC)Fe0 species, and treatment of 2a,b with 1 atm of CO led to the formation of (L)Fe(CO)4. Complex 2a was found to react with 1-azidoadamantane, giving rise to the dinuclear tetrazene complex (IMes)Fe(μ-NAd)2Fe(AdNNNNAd) (4).
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