The reaction of (beta-phenylethynyl)-pentafluorocydotriphosphazene, [(PhC C)(F)PN](PNF2)(2), with Fe-2(CO)(9) in refluxing hexane resulted in five new compounds, namely, [Fe(CO)(2){eta(2):eta(2)-2,4-(P3N3F5)(2)Ph2C4Fe(CO)(3)}-mu-CO] (1), [Fe(CO)(2){eta(2):eta(2)-2,5-(P3N3F5)(2)Ph2C4Fe(CO)(3)}-mu-CO] (2), [Fe(CO)(2){eta(5)-2,5-(P3N3F5)(2)Ph2C4CO}C-(Ph)=C(P3N3F5)](3), [Fe(CO)(3){eta(2):eta(2) -2,4-(P3N3F5)(2)-Ph2C4CO] (4), and [Fe(CO)(3){eta(2): eta(2)-2,5-(P3N3F5)(2)Ph2C4CO] (5). While compounds 1, 2, 4, and 5 have five-membered ferracyclopentadiene or cyclopentadienone rings coordinated to the Fe(CO)(3) unit in the eta(2):eta(2) mode, compound 3 has a 2,5-cyclopentadienone ring attached to an Fe(CO)(2)(P3N3F5)C=C(Ph) unit, where Fe is eta(5)-bonded to the cyclopentadienone ring, and the carbon that is a to the phenyl unit of the Fe(CO)(2)(P3N3F5)C=C(Ph) group is sigma-bonded to the oxygen atom of the cydopentadienone ring. Formation of five-membered cyclic compounds having two fluorophosphazene units on the vicinal carbon atoms of C4R2R'Y-2 rings was not observed in this reaction. No examples of Fe(CO)(3)-bound cyclobutadiene complexes were also isolated from this reaction. A similar reaction in the presence of trimethylamine N-oxide, NMe3O, was found to proceed at -20 degrees C with the formation of compounds 4 and 5 only. In contrast to the Fe-2(CO)(9) reaction, a reaction of alkyne-derived pentafluorocyclotriphosphazenes, [(RC C)(F)PN](PNF2)(2) [R = Ph, Fe(C5H5)(2)] with the molybdenum complex Cp(CO)(3)Mo-Mo(CO)(3)Cp (Cp = cydopentadienyl) in refluxing toluene resulted in the simple tetrahedral clusters Cp(CO)(2)Mo(P3N3F5)C-C(Ph)Mo(CO)(2)Cp (6) and Cp(CO)(2)Mo(P3N3F5)C-C(Fc)Mo(CO)(2)Cp (7) (Fc = ferrocenyl). A similar reaction of Cp(CO)(3)Mo Mo(CO)(3)Cp with butadiyne-derived fluorophosphazenes, [(RC C-C C)(F)PN](PNF2)(2) [R = Ph, Fe(C5H5)(2)], yielded the tetrahedral clusters Cp(CO)(2)Mo(P3N3F5)C-C(C CPh)Mo(CO)(2)Cp (8) and Cp(CO)(2)Mo(P3N3F5)C-C(C CFc)Mo(CO)(2)Cp (9) with the tetrahedral Mo2C2 unit forming exclusively with the alkyne unit of the butadiyne group bound to the cyclophosphazene ring. The crystal structures and infrared spectral data of these molybdenum clusters showed the presence of a semibridging carbonyl on one of the molybdenum units. All new compounds were characterized by IR, NMR {H-1}, C-13{H-1), (31)p{H-1}, and F-19{H-1}] and high-resolution mass spectrometry studies. Compounds 2, 3, 5, and 7-9 were also structurally characterized using single-crystal X-ray diffraction studies.