The iron half-sandwich [Cp'Fe(mu-I)](2) (Cp' = 1,2,4-(Me3C)(3)C5H2, 1) reacts with the pseudohalides NCO-, SCN-, SeCN- and N-3(-) to give [Cp'Fe(mu-NCO)](2) (2), [Cp'Fe(mu-S)](2) (3), [Cp'Fe(mu-Se-2)](2) (4) and [Cp'Fe(mu-N)](2) (5), respectively. Various spectroscopic techniques including X-ray diffraction, solid-state magnetic susceptibility studies and Fe-57 Mossbauer spectroscopy were employed in the characterization of these species. Mossbauer spectroscopy shows a decreasing isomer shift with increasing formal oxidation state, ranging from Fe(II) to Fe(IV), in complexes 1 to 5. The sulfido-bridged dimer 3 exhibits strong antiferromagnetic coupling between the Fe(III) centers. This leads to temperature-independent paramagnetism (TIP) at low temperature, from which the energy gap between the ground and the excited state can be estimated to be 2J = ca. 700 cm(-1). The iron(IV) nitrido complex [Cp'Fe(mu-N)](2) (5) shows no reactivity towards H-2 (10 atm), but undergoes clean reactions with CO (5 bar) and XylNC (Xyl = 2,6-Me2C6H3) to form the diamagnetic isocyanate and carbodiimide complexes [Cp'Fe(CO)(2)(NCO)] (7) and [Cp'Fe(CNXyl)(2)(NCNXyl)] (8), respectively. All compounds were fully characterized, and density functional theory (DFT) computations provide useful insights into their formation and the electronic structures of complexes 3 and 5.