The molybdenum(II) and tungsten(II) complexes [MCp2L] (Cp = eta (5)-cyclopentadienyl; L = C2H4, CO) react with perfluoroalkyl iodides to give a variety of products. The Mo(II) complex [MoCp2(C2H4)] reacts with perfluoro-n-butyl iodide or perfluorobenzyl iodide with loss of ethylene to give the first examples of fluoroalkyl complexes of Mo(IV), MoCp2(CF2CF2CF2CF3)I (8) and MoCp2(CF2C6F5)I (9), one of which (8) has been crystallographically characterized. In contrast, the CO analogue [MoCp2(CO)I reacts with perfluorobenzyl, iodide without loss of CO to give the crystallographically characterized salt, [MoCp2(CF2C6F5)(CO)I+I- (10), and the W(II) ethylene precursor [WCP2(C2H4)] reacts with perfluorobenzyl iodide without loss of ethylene to afford the salt [WCp2(CF2C6F5)(C2H4)1(+)I(-) (11). These observations demonstrate that the metal-carbon bond is formed first. In further contrast the tungsten precursor [WCP2(C2H4)] reacts With perfluoro-n-butyl iodide, perfluoro-iso-propyl iodide, and pentafluorophenyl iodide to give fluoroalkyl- and fluorophenyl-substituted cyclopentadienyl complexes WCp(eta (5)-C5H4RF)(H)I (12, R-F = CF2CF2CF2CF3; 15, R-F = CF(CF3)(2); 16, R-F = C6F5); the Mo analogue MoCp(eta (5)-C5H4RF)(H)I (14, R-F = CF(CF3)(2)) is obtained in similar fashion. The tungsten(IV) hydride compounds react with iodoform to afford the corresponding diiodides WCp(eta (C5H4RF)-C-5)I-2 (13, R-F = CF2CF2CF2CF3; 18, R-F = CF(CF3)(2); 19, R-F = C6F5), two of which (13 and 19) have been crystallographically characterized. The carbonyl precursors [MCp2(CO)] each react with perfluoro-iso-propyl iodide without loss of CO, to afford the exo-fluoroalkylated cyclopentadiene M(II) complexes MCp(eta (4)-C5H5RF)(CO)I (21, M = Mo; 22, M = W); the exo-stereochemistry for the fluoroalkyl group is confirmed by an X-ray structural study of 22. The ethylene analogues [MCP2(C2H4)] react with perfluoro-tert-butyl iodide to yield the products MCp2[(CH2CH2C(CF3)(3)]I (25, M = Mo; 26, M = W) resulting from fluoroalkylation at the ethylene ligand. Attempts to provide positive evidence for fluoroalkyl radicals as intermediates in reactions of primary and benzylic substrates were unsuccessful, but trapping experiments with CH3OD (to give RFD, not RFH) indicate that fluoroalkyl anions are the intermediates responsible for ring and ethylene fluoroalkylation in the reactions of secondary and tertiary fluoroalkyl substrates.