The synthesis and characterization of 14 monometallic derivatives of quinoline, quinoxaline, quinazoline and tetraazolo 1,5-A quinoline and a bimetallic derivative of quinoxaline are reported. These species were prepared in 11 to 88% isolated yields by metathesis reactions between NaFp or NaFp (where Fp = (η 5 -- C 5 H 5 )Fe(CO) 2 and Fp = (η 5 - indenyl)Fe(CO) 2 ) and the appropriate chlorine substituted polyaromatic azines. These reactions are highly regioselective and generally produce a single organometallic product having the organometallic substituent(s) bonded to the more highly activated azine ring. The structures of three representative examples were confirmed by their X-ray crystal structures, which are reported for the title complexes 4-[(η 5 -cyclopentadienyl)irondicarbonyl]-7-chloroquinoline (C 1 6 H 1 0 ClFeNO 2 ; a = 7.608(1) 9, b = 12.006(1) 9, b = 15.664(1) 9, V = 1431 9 3 ; orthorhombic; P2 1 2 1 2 1 ; Z = 4), 2-[(η 5 -cyclopentadienyl)irondicarbonyl]-3-chloroquinoxaline (C 1 5 H 9 ClFeN 2 O 2 ; a = 15.291(3) 9, b = 6.561(2) 9, c = 14.541(4) 9, β = 106.891(21)°, V = 1395.9 9 3 ; monoclinic; P2 1 /c; Z = 4), and 2-[(η 5 -indenyl)irondicarbonyl]-3-chloroquinoxaline (C 1 9 H 1 1 ClFeN 2 O 2 ;a = 19.131(2) 9, b = 6.688(1) 9, c = 13.515(2) 9, β = 101.569(11)°, V = 1694.1 9 3 ; monoclinic; P2 1 /c; Z = 4). The bimetallic quinoxaline derivative 2,3-[(C 5 H 5 ) 2 Fe 2 (CO) 4 ]-quinoxaline has ortho-substituted organometallic groups and the spectroscopic data suggest that it has an unusual structure in solution, perhaps involving bridging cyclopentadienyl and carbonyl ligands.