A series of manganese, iron and cobalt complexes bearing sterically demanding 1,3-disubstituted indenyl ligands, 1,3-(Me3C)2C9H5 (IndtBu) (1) and 1,3-(C6H11)2C9H5 (IndcHexyl) (2), has been prepared. These complexes have been fully characterised by various spectroscopic techniques, elemental analysis, and X-ray diffraction experiments. In addition the electronic and steric properties of these ligands have been evaluated. Although the cone angles and electronic properties are similar to 1,2,4-(Me3C)3C5H2 (Cp′), indenyl iron half-sandwich complexes are only stable at low temperature. This has been demonstrated for 1-FeI using suitable trapping experiments such as CO or NaCp′ addition to yield 1-Fe(CO)2I and 1-FeCp′, respectively. Overall the metal–ligand bonds in these indenyl compounds are weaker than in the corresponding cyclopentadienyl derivatives. In addition, the bis(indenyl)manganese complexes, 1-Mn and 2-Mn, are high-spin, as established by solid state magnetic susceptibility studies in the temperature range 2–300 K.
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