Studies on the Condensation Pathway to and Properties of Diiron Azadithiolate Carbonyls

Abstract

Reaction of Fe 2 (SH) 2 (CO) 6 and HCHO, which gives Fe 2 [(SCH 2 ) 2 NH](CO) 6 in the presence of NH 3

Diiron Complexes with Pendant Phenol Group(s) as Mimics of the Diiron Subunit of [FeFe]‐Hydrogenase: Synthesis, Characterisation, and Electrochemical Investigation

“…Complexes 4a-c were prepared from the reaction of [Fe 2 (μ-S) 2 (CO) 6 ], which was prepared following the literature procedure, [25] with organic bromides (Schemes 2 and 3). As show in Scheme 2, the three aromatic bromides were prepared by bromination of derivatives of methylanisol.…”

Electrochemical Synthesis of Mono‐ and Disubstituted Diiron Dithiolate Complexes as Models for the Active Site of Iron‐Only Hydrogenases

“…[3][4][5][6][7][8][9][10][11] The First structural models were readily accessed by the substitution of two CO ligands with two CN -ligands in [Fe 2 (S 2 C 3 H 6 )(CO) 6 ] (1). [12][13][14] Several structural aspects of the iron-only hydrogenase active site have been modeled by diiron complexes bearing azadithiolate and related bridges, [15][16][17][18] a 2Fe3S core, [19,20] or chelating ligands. [21][22][23][24][25][26] Mimicking the catalytic activity of the hydrogenases turns out to be far more challenging.…”

Synthesis, characterization, and electrochemical properties of diiron azadithiolate complexes related to the active site of [FeFe]-hydrogenases

“…In order to mimic the active site of [FeFe]-hydrogenases, diiron azadithiolate complexes [(l-SCH 2 ) 2 NR]Fe 2 (CO) 6 have been prepared, either by reaction of (l-LiS) 2 Fe 2 (CO) 6 (generated in situ from (l-S 2 )Fe 2 (CO) 6 and Et 3 BHLi in THF at -78°C) [1] with N,N-bis(chloromethyl)amines RN(CH 2 Cl) 2 or by sequential reaction of (l-SH) 2 Fe 2 (CO) 6 [2] with aqueous formaldehyde and primary amines [3]. Diiron azadithiolate complexes of the type [(l-SCH 2 ) 2 -NR]Fe 2 (CO) 5 (L), such as [(l-SCH 2 ) 2 NH]Fe 2 (CO) 5 (PPh 3 ) [4], [(l-SCH 2 ) 2 N(C 6 H 4 CO 2 Me-p)]Fe 2 (CO) 5 (PPh 3 ) [5], and [(l-SCH 2 ) 2 N(C 6 H 4 C : CC 6 H 4 NO 2 -4)]Fe 2 (CO) 5 (PPh 3 ) [6], were prepared by the substitution of carbonyl ligands with PPh 3 in the presence of Me 3 NO, and their properties were studied by cyclic voltammetric techniques.…”