Synthesis and characterization of carboxy-functionalized diiron model complexes of [FeFe]-hydrogenases: Decarboxylation of Ph2PCH2COOH promoted by a diiron azadithiolate complex

Diiron propanedithiolate complex bearing the pyridyl-functionalized phosphine ligand axially coordinated to a photosensitizer zinc tetraphenylporphyrin

“…A diiron propanedithiolate unit has two fused six-membered rings, in which one six-membered ring C8C7S1Fe2S2C9 has a boat conformation and another sixmembered ring C8C7S1Fe1S2C9 adopted a chair conformation. The pyridyl-functionalized phosphine ligand PyNHPPh 2 resides in an axial position of the square-pyramidal geometry of the Fe2 atom which is consistent with previously reported corresponding diiron dithiolate complexes with monophosphine ligands such as (m-PDT) Fe 2 (CO) 5 (Ph 2 PCH 2 COOH) [20], (m-PDT)Fe 2 (CO) 5 [Ph 2 PNHCH 2 CH 2 N(CH 3 ) 2 ] [21], and [(m-SCH 2 )CH(OH)]Fe 2 (CO) 5 (PPh 3 ) [22]. The Fe1-Fe2 bond length [2.5054(14) Å] is close to its parent complex (m-PDT)Fe 2 (CO) 6 [21], but shorter than those in the structures of natural enzymes Clostridium pasteurianum and Desulfovibrio desulfuricans (2.55e2.62 Å) [23,24].…”

Synthesis and structural characterization of iron–sulfur complexes with hydrophilic nitrogen–phosphorus ligands

“…4, complex 1 is composed of a typical butterfly [Fe 2 S 2 ] cluster ligated by a dithiolate ligand bridging the di-iron core, together with five carbonyls and one monophosphine ligand. The P(1) atom of the Ph 2 P(NHC 6 H 4 Cl) ligand resides in the apical site in the square pyramidal coordination geometry of the Fe(2) core, which is consistent with those reported in other phosphinemonosubstituted di-iron dithiolate complexes [30][31][32][33][34][35][36].…”

Synthesis, characterization and DFT studies of 1, 1′-Bis(diphenylphosphino)ferrocene substituted diiron complexes: Bioinspired [FeFe] hydrogenase model complexes

“…The geometry around the iron centres has been found to be distorted square pyramidal, which is common in [FeFe] H 2 ase model complexes. [56][57][58] In the crystal structure, two Fe atoms and two S atoms form a butterfly conformation as shown in the thermal ellipsoid plots ( figure 3).…”