The 19 electron complexes [FeI(cp)(C6R6)], R = H (1) or Me (2), cp =η5-C5H5, reduce CO2 in tetrahydrofuran to give [FeII(cp)(C6R6)]+, ½ CO32–, and ½ CO; in the presence of PMe3 and Na+PF6–, reduction of CO2 yields Na2CO3, [FeII(cp)(PMe3)3]+[PF6]–(3+), and [FeII(cp)(PMe3)2CO]+[PF6]–(4+) resulting from the reactions of the very electron-rich 19 electron species [FeI(cp)(PMe3)3](3).