The reaction of (eta5-C5Me5)(CO)2FeP=C(SiMe3)2 (1) with the isocyanides arylNC (2: aryl = Ph (a), 2-MeC6H4 (b), 2,6-Me2C6H3 (c)) in benzene at 20-degrees-C afforded the transition-metal-functionalized iminophosphiranes 3a-c as red crystalline solids. The novel compounds were characterized by elemental analyses and spectroscopic methods (IR, H-1, C-13, and P-31 NMR, and mass spectroscopy). The molecular structure of the iminophosphirane (eta5-C5Me5)(CO)2FePC-(SiMe3)2C=NPh (3a) was established by a complete single-crystal diffraction study (space group, C2/c; Z = 8, a = 27.214(4) angstrom, b = 15.146(2) angstrom, c = 15.854(2) angstrom, beta = 114.350(10)-degrees).