Iron(I)‐Based Carbonyl Complexes with Bridging Thiolate Ligands as Light‐Triggered CO Releasing Molecules (photoCORMs)

Abstract

A series of thiolate ligands were used to synthesize diiron(I) hexacarbonyl bis(thiolates) for structural studies. Conversion of the corresponding thiols with triiron(0) dodecacarbonyl yields complexes of the type [{(CO)3Fe(μ‐SR)}2] [R = C6H5 (1), C6H4‐4‐CH3 (2), C6H4‐4‐F (3), C6F5 (4), C6H4‐4‐CF3 (5), C6H2‐2,4,6‐(CH3)3 (6), CH2–C6H4‐4‐Cl (7)]. These complexes were isolated and fully characterized, including X‐ray crystal structures of complexes 2–7. The bridging thiolate ligands mainly influence the Fe–CO bond which is trans‐positioned to the second iron(I) center. In solution, the anti‐isomer with one axially and one equatorially oriented thiolate is the major species; severe steric strain induced by mesityl groups only allows the formation of syn‐endo‐isomeric molecules of 7. Furthermore, light‐induced CO release at solid material at the three representative complexes 1, 3, and 6 verify suitability as photoCORMs.

Synthesis, spectroscopic, CO‐releasing ability, and anticancer activity studies of [Mn(CO)3(L–L)Br] complexes: Experimental and density functional theory studies

“…In literature, several metal-based compounds are reported which are found to act as CORMs. [17][18][19] Nevertheless, they have several limitations such as poor solubility, spontaneous CO release triggered by either thermal factors or hydrolytic processes in aqueous medium, and toxicity due to the remaining dissociation products. [20] Recently, few manganese(I) tricarbonyl complexes have shown controlled CO release in the presence of irradiation.…”

[FeFe]‐Hydrogenase models featuring dithiolato‐bridgehead functionality: Preparation, structures, and electrocatalytic proton reduction

“…Based on the aforementioned informations, a great number of dithiolate dithiolate complexes as the active site models of [FeFe]‐hydrogenases were reported in the literatures [13–21] . Specially, some examples of diiron model complexes featuring dithiolate‐bridgehead functionality are particularly attractive becuase they can be easily achieved by the functional transformation reaction and display the catalytic proton reduction properties [22–28] .…”

“…[10][11][12] Based on the aforementioned informations, a great number of dithiolate dithiolate complexes as the active site models of [FeFe]-hydrogenases were reported in the literatures. [13][14][15][16][17][18][19][20][21] Specially, some examples of diiron model complexes featuring dithiolate-bridgehead functionality are particularly attractive becuase they can be easily achieved by the functional transformation reaction and display the catalytic proton reduction properties. [22][23][24][25][26][27][28] However, there are a litte attention concerning the influence of the dithiolato-bridgehead functionality on the structural and electrocatalytic behaviors of diiron model complexes.…”