Metal carbonyl analogues of iron–sulfur clusters found in metalloenzyme chemistry

Electron‐Rich Diferrous–Phosphane–Thiolates Relevant to Fe‐only Hydrogenase: Is Cyanide “Nature's Trimethylphosphane”?

“…Each consisted of a face-sharing bioctahedral core, not unlike previous members of this series of diferrous-dithiolates, that is, [Fe 2 (S 2 C 2 H 4 )(mCNMe)(CNMe) 6 ] 2 + , [15] [Fe 2 (S 2 C 2 H 4 )(m-CO)(CNMe) 6 ] 2 + , [22] and [Fe 2 (S 2 C 2 H 4 )(m-CO)(CN) 2 (CO) 2 (PPh 3 ) 2 ]. [23] The Fe À Fe distances fall in the range 2.5135(12)-2.6006(7) , comparable to other diferrous-thiolates as well as the Fe-only hydrogenase active site.…”

“…Research on the chemistry of diiron-carbonyl-dithiolates, [Fe 2 (m-SR) 2 (CO) 6 ], dates back to the 1920s with the preparation of the ethanethiol derivative. [1,2] Decades of subsequent work have demonstrated the versatility of this motif.…”

“…Recently, various states for the active site of the Fe-only hydrogenase enzymes were spectroscopically and structurally characterized and shown to contain strongly related diironcarbonyl-thiolates. [3][4][5] The structural biology presents many challenges to the basic chemistry of the diiron-dithiolates, [6] including coordination of a 4 Fe-4 S cluster, a novel dithiolate cofactor, [7] and the occurrence of CN À ligands. Many of these features are being addressed in an effort to develop structural and functional models for Fe-only hydrogenases active site.…”

One-pot synthesis of sulphur bridged dinuclear rhenium metallacycles via addition of S–S bond across Re–Re bond

“…1 H NMR spectra of compounds 1-9 displayed appropriate signals for the pyridine ligands and aryl groups bonded to bridging sulphur and the data of the compounds were given in experimental section. In 1 H NMR spectra of compounds 1, 4 and 7 displayed, one doublet, two triplets for pyridyl group (py) protons and phenyl group protons showed one doublet and two triplets.…”

“…Transition metal complexes containing the disulphide ligand exhibit a wide range of interesting reactivity and chelating ability at the sulphur atoms [1][2][3][4][5][6][7][8]. Metal sulphides are of interest due to their wide application in various platforms, such as, catalyst for the removal of organosulphur compounds from the feedstock [9,10], as solid state lubricant [11], as good electrical conductor [12][13][14][15] and for their role in NO storage and transport in vivo to stabilize therapeutic protein structures in the biological processes [16][17][18].…”