Syntheses, crystal structures, and electrochemical studies of diiron complexes from the reactions of [Et 3 NH][(μ-RS) Fe 2 (CO) 6 (μ-CO)] with isothiocyanates

Reactions of [Et 3 NH][(μ-MeO 2 CCH 2 S)Fe 2 (CO) 6 (μ-CO)] in situ generated from the mixture of MeO 2 CCH 2 SH, Et 3 N, and Fe 3 (CO) 12 with 2-C 5 H 4 NNCS, 3-C 5 H 4 NNCS, and EtNCS in THF, form 1 , (μ-MeO 2 CCH 2 S)Fe 2 (CO) 5 (μ-k 2 N,S:k 2 C-2-C 5 H 4 NNHCS), 2 , (μ-MeO 2 CCH 2 S)Fe 2 (CO) 6 (μ-k 2 C,S-3-C 5 H 4 NNHCS), and 3 , (μ-MeO 2 CCH 2 S)Fe 2 (CO) 6 (μ-k 2 C,S-EtNHCS). Reaction of [Et 3 NH][(μ-PhS)Fe 2 (CO) 6 (μ-CO)] in situ formed from the mixture of PhSH, Et 3 N, and Fe 3 (CO) 12 with EtNCS affords 4 , (μ-PhS)Fe 2 (CO) 6 (μ-k 2 C,S-EtNHCS).

Reaction of [Et 3 NH][(μ-EtS)Fe 2 (CO) 6 (μ-CO)] in situ produced from the mixture of EtSH, Et 3 N, and Fe 3 (CO) 12 with EtNCS offers 5 , (μ-EtS)Fe 2 (CO) 6 (μ-k 2 C,S-EtNHCS). All new complexes have been fully characterized by EA, IR, 1 H NMR, and 13 C NMR and structurally determined by X-ray crystallography. Electrochemical studies on 2 and 5 confirm that 2 shows high H 2 -producing activity.