69346-73-2

Upstream product

• 38117-54-3 cyclopentadienyl iron(II) dicarbonyl dimer 
• 88333-03-3 Benzyl isocyanide 

Relevant academic research and scientific papers

Easily Available, Amphiphilic Diiron Cyclopentadienyl Complexes Exhibit in Vitro Anticancer Activity in 2D and 3D Human Cancer Cells through Redox Modulation Triggered by CO Release

A straightforward two-step procedure via single CO removal allows the conversion of commercial [Fe2Cp2(CO)4] into a range of amphiphilic and robust ionic complexes based on a hybrid aminocarbyne/iminium ligand, [Fe2Cp2(CO)3{CN(R)(R’)}]X (R, R’=alkyl or aryl; X=CF3SO3 or BF4), on up to multigram scales. Their physicochemical properties can be modulated by an appropriate choice of N-substituents and counteranion. Tested against a panel of human cancer cell lines, the complexes were shown to possess promising antiproliferative activity and to circumvent multidrug resistance. Interestingly, most derivatives also retained a significant cytotoxic activity against human cancer 3D cell cultures. Among them, the complex with R=4-C6H4OMe and R’=Me emerged as the best performer of the series, being on average about six times more active against cancer cells than a noncancerous cell line, and displayed IC50 values comparable to those of cisplatin in 3D cell cultures. Mechanistic studies revealed the ability of the complexes to release carbon monoxide and to act as oxidative stress inducers in cancer cells.

Regioselective Nucleophilic Additions to Diiron Carbonyl Complexes Containing a Bridging Aminocarbyne Ligand: A Synthetic, Crystallographic and DFT Study

Diiron μ-aminocarbyne compounds, 1a–e, are prepared in two steps from Fe2Cp2(CO)4, negating the need for difficult purification procedures of intermediate species; they are efficiently isolated by alumina chromatography. Minor amounts of μ-aminocarbyne aryl isocyanide compounds, 2a–c, are obtained as side products. The structures of the cations in 1a,c,e are calculated using DFT; the carbyne carbon is generally predicted to be the thermodynamic site of hydride addition, in agreement with a previous experimental finding concerning 1a. Accordingly, the reaction of 1e with NaBH4 affords a bridging aminocarbene complex, 4, in 85 % yield. Otherwise, the reaction of 1c with NaBH4 yields the aminocarbyne–cyclopentadiene derivative 3 (70 %), presumably as a consequence of the steric protection exerted by the xylyl–methyl groups towards the carbyne moiety. The sequential treatment of 1a,c with Li2CuCNMe2 and MeSO3CF3 affords 5a,b, comprising both aminocarbyne and alkoxycarbene ligands. In accordance with DFT calculations, the alkoxycarbene moiety in 5a is the most favourable site for nucleophilic attack. Thus, the reactions of 5a with NH2R (R = Et, iPr) and NBu4CN, respectively, give the aminocarbyne/aminocarbene complexes, 6a,b, and the aminocarbyne-α-cyanoalkyl 7. All the products are fully characterized by spectroscopic and analytical methods; moreover, the structures of 1a, 1d, 6a and 7 are elucidated by single-crystal X-ray diffraction studies.