Reactions of [Fe<sub>6</sub>C(CO)<sub>14</sub>(S)]<sup>2</sup><sup>–</sup>: Cluster Growth, Redox, Sulfiding
Liang Liu, Toby J. Woods, Thomas B. Rauchfuss
Abstract
Redox reactions, substitutions, and metalations are reported for the iron carbido sulfide [Fe 6 C(CO) 14 (S)] 2– ([ 1 ] 2– ). Dianion [ 1 ] 2– oxidized to [Fe 6 C(CO) 16 (S)] 0 ([ 2 ] 0 ) upon treatment with of [Fe(C 5 H 5 ) 2 ]BF 4 or HBF 4 (H 2 formation) under an atmosphere of CO. Reaction of [ 2 ] 0 with t BuNC gave [Fe 6 C(S)(CO) 13 ( t BuNC) 5 ], consisting of Fe 5 C(CO) 13 and [Fe( t BuNC) 5 ] 2+ subunits linked by a µ 3 ‐S 2– . The Fe 7 CS cluster [Fe 7 C(CO) 17 (S)] 2– formed upon treatment of (Ph 4 P) 2 [ 1 ] with Fe(benzylideneacetone)(CO) 3 . The Fe 7 species is an edge‐fused cluster with [Fe 6 C(CO) 10 (µ‐CO) 4 ] and Fe(CO) 3 subunits joined by µ 3 ‐S and two Fe–Fe bonds. The analogous reaction using Mo(CO) 4 (norbornadiene) gave [MoFe 6 C(CO) 18 (S)] 2– . In this cluster, the Mo center is located in the octahedral subunit. Treatment of [ 1 ] 2– with SO 2 afforded [Fe 6 C(S)(SO 2 )(CO) 13 ] 2– . This cluster features an Fe 6 C core decorated with µ 3 ‐S and µ 2 ‐SO 2 ligands. These experiments were undertaken in an effort to connect organometallic clusters to FeMoco.