The Active Site Model for Iron-Only Hydrogenases Coordinatively Bonded to a Metalloporphyrin Photosensitizer

Treatment of the parent model [(μ-SCH2)2NH]Fe2(CO)6 (1) with 4-pyridinecarboxylic acid chloride or benzoyl chloride in the presence of Et3N afforded the simple model compounds [(μ-SCH2)2NC(O)C5H4N]Fe2(CO)6 (2) and [(μ-SCH2)2NC(O)Ph]Fe2(CO)6 (4). Further treatment of 2 with the photosensitizer zinc tetraphenylporphyrin (ZnTPP) produced the target model compound [(μ-SCH2)2NC(O)C5H4N]Fe2(CO)6(ZnTPP) (3), which is the first metalloporphyrin-containing active site model for the Fe-only hydrogenases.