A new transition metalate system, [(η 5 -Me 3 SiC 5 H 4 )Fe(CO)(PPh 3 )] -M þ (SiFpPM; M = Li, Na), was synthesized via treatment of (η 5 -C 5 H 5 )Fe(CO)(PPh 3 )SiMe 3 with sodium and lithium diisopropylamides (MN(iPr 2 ); NADA and LDA, respectively). The utility of NADA was far superior to that of LDA, with shorter reaction times, lower reagent concentrations, and higher yields. Infrared spectroscopic analysis of the new ferrates indicated that their stability and utility were dependent upon the tight ion pairs Fe-CO-M; in the presence of coordinating solvents and ionophores the separated ion pairs formed led to the expulsion of the PPh 3 and CO scavenging led to formation of the dicarbonylferrate [(η 5 -Me 3 SiC 5 H 4 )Fe(CO) 2 ] -M þ . Hexane was the solvent of choice for formation and use of the ferrates. Reactions of the new ferrates with MeI led to [SiFpP]CH 3 , whereas reactions with ClCH 2 SiMe 2 R (R = H, SiMe 3 ) did not lead to the expected Fe-C bonded complexes [SiFpP]CH 2 SiMe 2 R but to high yields of the rearranged complexes [SiFpP]SiMe 2 CH 2 R. The presence of the thermally labile phosphine group readily produces a coordinatively unsaturated 16e species that permits Fe-CH 2 -SiMe 2 R to FeSiMe 2 CH 2 R rearrangements (previously observed photochemically with the simple Fp derivatives) to occur thermally.