The diiron ynamine complexes [Fe2(CO)7{μ-C(R)C(NEt2)}] (1) (R=Me, Ph, C3H5, SiMe3) react with theN-sulfinylaniline, PhNSO, in refluxing hexane to yield the complexes [Fe2(CO)6{μ-N(Ph)C(Me)S}] (2), [Fe2(CO)6{μ-N(Ph)C(NEt2)C(Ph)S}] · 0.5C6H12 (3), [Fe2(CO)6{μ-C(C3H5)C(NEt2)N(Ph)SO}] · 0.5CH2Cl2 (4), and [Fe2(CO)6{μ-C(SiMe3)C(NEt2)S)}] (5). Compound 5 was found to be identical to the previously reported product obtained from the reaction of 1 with sulfur. Compounds 2, 3, and 4 were characterized by single crystal X-ray diffraction analyses. Crystal data: for 2: space group = P21/n,a=9.533(1) A,b=18.830(4) A,c=12.705(4) A, β=107.01(2)°,Z=4, 2687 reflections,R=0.027; for 3: space group=P21/n,a=13.660(2) A,b=19.096(8) A,c=10.972(2) A, β=90.62(1)°,Z=4, 2821 reflections,R=0.036; for 4: space group=P21/a,a=18.098(5) A,b=16.564(4) A,c=18.548(2) A, β=115.44(2)°,Z=4, 3569 reflections,R=0.041. Complexes 2 and 3 result from fragmentation of theN-sulfinylaniline ligand and insertion of the nitrene grouping into the Fe=C(aminocarbene) bond, whereas the sulfur atom inserts into one Fe-C bond of the bridging carbene. Compound 4 is formed by insertion of the entireN-sulfinyl aniline ligand into the Fe=C(aminocarbene) bond. All three complexes have basket-like arachno structure isolobal to the benzvalene one.