Organometallic Allene [(μ‐C)(Fe(CO)4)2]: Bridging Carbon Showing Transformation from Classical Electron‐Sharing Bonding to Double σ‐Donor and Double π‐Acceptor Ligation

Abstract

AbstractAllenes (R2C=C=CR2) have been traditionally perceived to feature localized orthogonal π‐bonds between the carbon centres. We have carried out quantum‐mechanical studies of the organometallic allenes envisioned by the isolobal replacement of the terminal CH2 groups by the d8 Fe(CO)4 fragment. Our studies have identified two organometallic allenes viz. D2d symmetric [(μ‐C)(Fe(CO)4)2] (2) and D3 symmetric [(μ‐C)(Fe(CO)4)2] (3) with trigonal bipyramidal coordination at the Fe atoms. Compound 2 features the bridging carbon atom in an equatorial position with respect to the ligands on the TM centre, while 3 features the central carbon atom in an axial position. The bis‐pseudoallylic anionic delocalisation proposed in the C2‐C1‐C3 spine of organic allene is retained in the organometallic allene 2, and is transformed to a typical three‐centre bis‐allylic anionic delocalisation in the organometallic allene 3. The topological analysis of electron density also indicates a bis‐allylic anionic type delocalisation in the organometallic allenes. The quantitative bonding analysis using the EDA‐NOCV method suggests a transition from classical electron‐sharing bonding between the central carbon atom and the terminal groups in 1 to donor‐acceptor bonding in 3. Meanwhile, both electron‐sharing and donor‐acceptor bonding models are found to be probable heuristic bonding representations in the organometallic allene 2.