Abstract
The reaction of Fe(2,6-xylylNC) 3( iPr-DAB) ( 5) with carbon disulfide and carbonyl sulfide yields bicyclic structures. The reaction with carbon disulfide proceeds via a 1,3-dipolar cycloaddition of the C=S bond across the FeN=C unit, followed by an isocyanide insertion to form the ferra[2.2.2]bicyclic complex ( 8). A single crystal X-ray structure determination on ( 8)showed it to contain three six-membered rings; the carbon disulfide is attached to the central metal atom through a sulphur atom and to the former imine carbon atom through its central carbon atom. In the 1,3-dipolar cycloaddition of carbonyl sulfide the presence of moisture resulted in a protonation of the amido function. This inhibits the isocyanide insertion and stabilizes the initially formed ferra[2.2.1]-bicyclic compound.
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