Reactions of [Fe6C(CO)14(S)]2–: Cluster Growth, Redox, Sulfiding.

Redox reactions, substitutions, and metalations are reported for the iron carbido sulfide [Fe6C(CO)14(S)]2– ([1]2–). Dianion [1]2– oxidized to [Fe6C(CO)16(S)]0 ([2]0) upon treatment with of [Fe(C5H5)2]BF4 or HBF4 (H2 formation) under an atmosphere of CO. Reaction of [2]0 with tBuNC gave [Fe6C(S)(CO)13(tBuNC)5], consisting of Fe5C(CO)13 and [Fe(tBuNC)5]2+ subunits linked by a µ3‐S2–. The Fe7CS cluster [Fe7C(CO)17(S)]2– formed upon treatment of (Ph4P)2[1] with Fe(benzylideneacetone)(CO)3. The Fe7 species is an edge‐fused cluster with [Fe6C(CO)10(µ‐CO)4] and Fe(CO)3 subunits joined by µ3‐S and two Fe–Fe bonds. The analogous reaction using Mo(CO)4(norbornadiene) gave [MoFe6C(CO)18(S)]2–. In this cluster, the Mo center is located in the octahedral subunit. Treatment of [1]2– with SO2 afforded [Fe6C(S)(SO2)(CO)13]2–. This cluster features an Fe6C core decorated with µ3‐S and µ2‐SO2 ligands. These experiments were undertaken in an effort to connect organometallic clusters to FeMoco. [ABSTRACT FROM AUTHOR]