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

Treatment of the parent model [(μ-SCH 2 ) 2 NH]Fe 2 (CO) 6 ( 1 ) with 4-pyridinecarboxylic acid chloride or benzoyl chloride in the presence of Et 3 N afforded the simple model compounds [(μ-SCH 2 ) 2 NC(O)C 5 H 4 N]Fe 2 (CO) 6 ( 2 ) and [(μ-SCH 2 ) 2 NC(O)Ph]Fe 2 (CO) 6 ( 4 ). Further treatment of 2 with the photosensitizer zinc tetraphenylporphyrin (ZnTPP) produced the target model compound [(μ-SCH 2 ) 2 NC(O)C 5 H 4 N]Fe 2 (CO) 6 (ZnTPP) ( 3 ), which is the first metalloporphyrin-containing active site model for the Fe-only hydrogenases.