Carbene ligands in diiron complexes

The diiron frame Fe2Cp2CO2 allows the coordination of a variety of carbene ligands, including heteroatom substituted (Fischer type) and alkylidenes, in both bridging and terminal coordination modes. Synthetic strategies have been devised for obtaining aminocarbenes and thiocarbenes, by nucleophilic addition on the corresponding bridging amino- and thio-carbyne cationic complexes [Fe2(μ-CX)(μ-CO)(CO)2(Cp)2][SO3CF3] (X = SMe, NMe2, N(Me)Xyl), respectively. A more general approach to the synthesis of diiron complexes bridged by carbenes, exploits the electrophilic character of the sulphonium complex [Fe2{μ-C(CN)(SMe2)}(μ-CO)(CO)2(Cp)2][SO3CF3] and the facile displacement of the SMe2 moiety by nucleophiles. These methods afford a large variety of heteroatom (N, P, O, S) substituted carbene complexes and also μ-alkylidenes.Terminally bonded alkynyl methoxy carbene complexes have been obtained by the classical Fischer method, consisting in nucleophilic addition at a terminal CO, to generate an acyl intermediate, followed by oxygen atom methylation. The coordination to diiron cationic complexes makes the alkynylmethoxy carbene ligands very reactive towards the addition of nucleophiles, like amines and carbanions. These additions are regio- and stereoselective, occurring exclusively at the alkynyl moiety.Finally, new multidentate and functionalized bridging ligands are described. They are anchored to the diiron frame through an aminocarbene, or an alkylidene binding end, or both. These ligands result from intramolecular couplings and rearrangements which involve the μ-aminocarbyne, the terminally bonded nitrile ligands and acetylides.

Graphical abstractThe diiron frame Fe2Cp2(CO)2 provides an efficient support for the coordination a variety of heteroatom substituted carbene ligands, both bridging (e.g., I) and terminal (e.g., II). These have been obtained from diiron μ-carbyne precursors. Insertion reactions, nucleophilic additions, and intramolecular couplings of coordinated ligands in these diiron complexes afford new multidentate ligands displaying carbene character (e.g., III).Figure optionsDownload full-size imageDownload as PowerPoint slide