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A CO2 complex of iron(0), Fe(CO2)(depe)2 (1; depe = 1,2-bis(diethylphosphino)ethane) has been prepared by replacement of N2 in Fe(N2)(depe)2 by CO2. The X-ray structure analysis of 1 shows that it has a η2(C,O)-CO2 ligand in a trigonal-bipyramidal Fe geometry with some contribution of an η1(C) mode. Reaction of 1 with R3SnCl in Et2O at −78 °C gives the iron carboxylate complexes FeCl(CO2SnR3)(depe)2 (R = Me, (2a), Ph (2b)). The X-ray structure analysis of 2b shows that the CO2 fragment bridges between the Fe and Sn atoms in a μ-η1(C):η2(O,O‘)-CO2 fashion. Treatment of 1 with Me3SiCl results in the removal of an O atom from the CO2 ligand to give a cationic carbonyliron(II) complex, [FeCl(CO)(depe)2]+Cl- (3a), and (Me3Si)2O. Similarly, 1 reacts with carbon electrophiles such as MeI and MeOTf to give the corresponding cationic iron(II) carbonyl complexes [FeX(CO)(depe)2]+X- (X = I (3b), OTf (3c)) and Me2O.

Reaction of [Fe(N2)(depe)2] with carbon dioxide gives trigonal bipyramidal [Fe(q2-C02)(depe)2], where the coordinated COP lies on equatorial plane by an q2-fashion and converts into dimethyl ether and [FeX(CO)(depe)2]X (X = I, OTf) on interaction with methyl halide or triflate.

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