Mononuclear Iron(II) Dicarbonyls Derived from NNS Ligands – Structural Models Related to a “Pre‐Acyl” Active Site of Mono‐Iron (Hmd) Hydrogenase

Muthiah, Keren A. Thomas; Durgaprasad, Gummadi; Xie, Zhu‐Lin; Williams, Owen M.; Joseph, Chris; Lynch, Vincent M.; Rose, Michael J.

doi:10.1002/ejic.201403013

Cited by 18 publications

(21 citation statements)

References 36 publications

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“…The band at 2097 cm −1 increased in intensity whilst the bands at 2050 and 1978 cm −1 decreased in intensity over the course of the reaction. The bands at 2050 and 1978 cm −1 are most likely associated with terminal Fe carbonyls 63 and occur in a similar range to those of the Fe II carbonyl species, (η 2 -2,6-Dipp 2 C 6 H 3 CO) 2 Fe(CO) 2 , ( ν = 2000, 1944 cm −1 ) 48 , whilst the band at 2097 cm −1 is consistent with a ketene or ketenyl species (C=C=O), which appear in the range 2080 to 2250 cm −1 62 . The reaction between 1 Mes and 13 CO was also monitored by IR spectroscopy (Fig.…”

Section: Resultsmentioning

confidence: 98%

Selective reduction and homologation of carbon monoxide by organometallic iron complexes

et al. 2018

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Carbon monoxide is a key C1 feedstock for the industrial production of hydrocarbons, where it is used to make millions of tonnes of chemicals, fuels, and solvents per annum. Many transition metal complexes can coordinate CO, but the formation of new C−C bonds in well-defined compounds from the scission and subsequent coupling of two or more CO moieties at a transition metal centre remains a challenge. Herein, we report the use of low-coordinate iron(II) complexes for the selective scission and homologation of CO affording unusual squaraines and iron carboxylates at ambient temperature and pressure. A modification of the ligand framework allows for the isolation and structural characterisation of a proposed metallacyclic Fe(II) carbene intermediate. These results indicate that, with the appropriate choice of supporting ligands, it is possible to cleave and homologate carbon monoxide under mild conditions using an abundant and environmentally benign low-coordinate, first row transition metal.

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Section: Resultsmentioning

confidence: 98%

Selective reduction and homologation of carbon monoxide by organometallic iron complexes

et al. 2018

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“…Please note that the intensities of the spectra of the parent complexes were purposely reduced to allow clear observations of the bands from those intermediates 2,033 cm −1 (solid state). [46,48] Therefore, for the bromo analogues (3 and 4), no tribromo species was detected. Most likely, the spectroscopically detected intermediates are analogously assigned to those containing Fe(cis-CO) 2 core.…”

Section: F I G U R E 3 Ortep Diagram Of Complexmentioning

confidence: 90%

Four iron(II) carbonyl complexes containing both pyridyl and halide ligands: Their synthesis, characterization, stability, and anticancer activity

Guo

Jin

Xiao

et al. 2020

Applied Organom Chemis

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Four iron(II) carbonyl complexes, fac-[Fe (CO) 3 X 2 (py)] (X = I − , 1 and Br − , 3), fac-[{Fe (CO) 3 X 2 } 2 (bipy)] (X = I − , 2 and Br − , 4), were facilely synthesized by reacting cis-[Fe (CO) 4 X 2 ] (X = I − , Br −) with pyridine (py) and 4,4 0-dipyridine (bipy) ligands, respectively, in good yields (70%85%). These complexes were fully characterized, and the structures of Complexes 2 and 3 were crystallographically analyzed. In dimethyl sulfoxide, they decomposed rapidly to release carbon monoxide (CO), and in methanol, they showed better stability which allowed kinetically analyzing their decomposing behaviors. The selfdecomposing in methanol fitted first-order kinetics with a half-time ranging from several minutes to 1 h. Our results suggested that the ligand with great conjugation (bipy) and strong electron-donating capability (iodide) could stabilize the iron(II) carbonyl complexes. The decomposition of the iodo complexes (1 and 2) involved the production of iodine radicals. MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide) assessments revealed that the efficacy against human bladder carcinoma cell line (RT112) is in the following trend: 1 > 2 > 3 > 4. The relatively strong efficacy of Complexes 1 and 2 is mainly contributed to the in situ generated iodine radicals. The combination of the cytotoxicity of the in situ generated radicals with the anticancer activity of CO as reported in literatures may lead to developing novel anticancer drugs with enhanced efficacy. K E Y W O R D S anticancer activity, carbon monoxide release and kinetics, iodine radical, iron carbonyl compounds, solvolysis Zhuming Guo and Jing Jin contributed equally to this work.

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“…Rose and his group are interested in the development of synthetic models of monoiron hydrogenase, and also fundamental electron transfer phenomena, as well as the attachment of molecules or materials to light absorbers such as silicon and gallium phosphide. He has reported in the European Journal of Inorganic Chemistry on mononuclear iron(II) dicarbonyl species …”

Section: Awarded …mentioning

confidence: 99%

2016 Cottrell Scholars: W. C. K. Pomerantz, M. J. Rose, T. J. Maimone, and Y. Yu / Honorary Doctorate: H. J. Freund

2016

Angew Chem Int Ed

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Mononuclear Iron(II) Dicarbonyls Derived from NNS Ligands – Structural Models Related to a “Pre‐Acyl” Active Site of Mono‐Iron (Hmd) Hydrogenase

Abstract: We report the syntheses and characterization of dicarbonyliron complexes derived from tridentate, ortho-substituted Schiff base pyridine/thioether ligands ( R NNS). Metalation reactions of R NNS (R = CH 3 , OCH 3 ) at low temperature (-78°C) with [Fe(CO)

Cited by 18 publications

References 36 publications

Selective reduction and homologation of carbon monoxide by organometallic iron complexes

Selective reduction and homologation of carbon monoxide by organometallic iron complexes

Four iron(II) carbonyl complexes containing both pyridyl and halide ligands: Their synthesis, characterization, stability, and anticancer activity

2016 Cottrell Scholars: W. C. K. Pomerantz, M. J. Rose, T. J. Maimone, and Y. Yu / Honorary Doctorate: H. J. Freund

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