The alkyl compounds [Cp*Fe(CO) 2 R] have been synthesized by the reaction of Na[Cp*Fe(CO) 2 ] with the appropriate n-alkyl chloride or bromide (Cp*=η 5 -C 5 (CH 3 ) 5 ; R=n-C 3 H 7 to n-C 1 2 H 2 5 ). The majority of the compounds are new and have been fully characterized by microanalysis, IR, 1 H-, and 1 3 C-NMR and mass spectrometry. The data are discussed and some properties of the compounds are described. The X-ray crystal and molecular structure of [Cp*Fe(CO) 2 (n-C 5 H 1 1 )] has been determined. The compound forms monoclinic crystals in the space group P2 1 /c and has a Fe C(alkyl) bond length of 2.07 9. The structure and β-hydride elimination of [CpFe(CO) 2 (CH 2 CH 3 )] are investigated by ab initio molecular orbital (MO), MP2 and density functional (DFT) calculations.