The new 2,4,6-trimethylaniline complexes [Cp
(CH
3
)
3
)]
+
(4) (Cp
⁄
= g
5
-C
5
(CH
3
)
5
;Cp=g
5
-C
5
H
5
⁄
Fe(CO)
2
(NH
2
C
6
H
2
(CH
3
)
3
)]
(3) and [CpFe(CO)
) have been synthesized and isolated in high yields as tetrafluoroborate salts. They have been fully characterized by NMR, IR, elemental analysis, thermogravimetric analysis and X-ray crystallography. For comparison purpose, the molecular structure of [CpFe(CO)
2
(NH
2
CH
2
C
6
H
4
OCH
3
)]
+
(5) has been determined and discussed in relation to those of 3 and 4. Compounds 3 and 5 crystallize in monoclinic P2
1
/c space group, while 4 crystallizes in triclinic P 1 space
group. Compounds 3 and 4 exhibited considerable thermal stabilities at temperatures as high as 170 C, which is close to their melting points.
2
(NH
2
C
6
H
2