Synthesis and Characterization of Stable Iron Pentacarbonyl Radical Cation Salts

Overview

Journal Angew Chem Int Ed Engl

Specialty Chemistry

Date 2022 May 11

PMID 35543697

Authors

Jan M Rall

Marcel Schorpp

Martin Keilwerth

Maximilian Maylander

Christian Friedmann

Michael Daub

Sabine Richert

Karsten Meyer

Ingo Krossing

Affiliations

Soon will be listed here.

Abstract

The open-shell iron pentacarbonyl cation [Fe(CO) ] was isolated by deelectronation, i.e., the single-electron oxidation of the parent neutral Fe(CO) using [phenazine ] as the [Al(OR ) ] and [F-{Al(OR ) } ] salt (R =C(CF ) ; phenazine =perfluoro-5,10-bis(perfluorophenyl)-5,10-dihydrophenazine). [Fe(CO) ] [Al(OR ) ] was fully characterized (scXRD analysis, IR, NMR, EPR, Fe spectroscopy, CV and SQUID magnetization study) and, apart from being a compound of fundamental interest, may serve as a precursor for low-valent iron coordination chemistry.

Citing Articles

Solvent-Dependent Reactivity of Fe(CO) under Superacidic and Oxidative Conditions.

Berg W, Reimann M, Sievers R, Rupf S, Schlogl J, Weisser K J Am Chem Soc. 2025; 147(4):3039-3046.

PMID: 39806569 PMC: 11783529. DOI: 10.1021/jacs.4c09595.

Isolation and characterization of the dimetal decacarbonyl dication [Ru(CO)] and the metal-only Lewis-pair [Ag{Ru(CO)}] .

Sellin M, Grunenberg J, Krossing I Dalton Trans. 2024; 54(6):2294-2300.

PMID: 39670835 PMC: 11640294. DOI: 10.1039/d4dt03364g.

A Caged Neutral 17-Valence-Electron Iron(I) Radical [Fe(CO)(Cl)(P((CH))P)]: Synthetic, Structural, Spectroscopic, Redox, and Computational Studies.

Zarcone S, Zhang Z, Handunneththige S, Ni Z, Bhuvanesh N, Nippe M Inorg Chem. 2024; 63(35):16313-16326.

PMID: 39163584 PMC: 11379347. DOI: 10.1021/acs.inorgchem.4c02275.

Pushing redox potentials to highly positive values using inert fluorobenzenes and weakly coordinating anions.

Armbruster C, Sellin M, Seiler M, Wurz T, Oesten F, Schmucker M Nat Commun. 2024; 15(1):6721.

PMID: 39112470 PMC: 11306567. DOI: 10.1038/s41467-024-50669-3.

Role of the Molecular Environment in Quenching the Irradiation-Driven Fragmentation of Fe(CO): A Reactive Molecular Dynamics Study.

Andreides B, Verkhovtsev A, Fedor J, Solovyov A J Phys Chem A. 2023; 127(17):3757-3767.

PMID: 37076805 PMC: 10165649. DOI: 10.1021/acs.jpca.2c08756.

References

Malinowski P, Krossing I . Ag[Fe(CO)5]2(+) : a bare silver complex with Fe(CO)5 as a ligand. Angew Chem Int Ed Engl. 2014; 53(49):13460-2. DOI: 10.1002/anie.201408019. View

Lemaire J, Boissel P, Heninger M, Mauclaire G, Bellec G, Mestdagh H . Gas phase infrared spectroscopy of selectively prepared ions. Phys Rev Lett. 2003; 89(27):273002. DOI: 10.1103/PhysRevLett.89.273002. View

Schmitt M, Maylander M, Goost J, Richert S, Krossing I . Chasing the Mond Cation: Synthesis and Characterization of the Homoleptic Nickel Tetracarbonyl Cation and its Tricarbonyl-Nitrosyl Analogue. Angew Chem Int Ed Engl. 2021; 60(27):14800-14805. PMC: 8251987. DOI: 10.1002/anie.202102216. View

Unkrig W, Schmitt M, Kratzert D, Himmel D, Krossing I . Synthesis and characterization of crystalline niobium and tantalum carbonyl complexes at room temperature. Nat Chem. 2020; 12(7):647-653. DOI: 10.1038/s41557-020-0487-3. View

Rall J, Schorpp M, Keilwerth M, Maylander M, Friedmann C, Daub M . Synthesis and Characterization of Stable Iron Pentacarbonyl Radical Cation Salts. Angew Chem Int Ed Engl. 2022; 61(32):e202204080. PMC: 9401057. DOI: 10.1002/anie.202204080. View

Farrugia L, Evans C . Experimental X-ray charge density studies on the binary carbonyls Cr(CO)6, Fe(CO)5, and Ni(CO)4. J Phys Chem A. 2006; 109(39):8834-48. DOI: 10.1021/jp053107n. View

Schorpp M, Heizmann T, Schmucker M, Rein S, Weber S, Krossing I . Synthesis and Application of a Perfluorinated Ammoniumyl Radical Cation as a Very Strong Deelectronator. Angew Chem Int Ed Engl. 2020; 59(24):9453-9459. PMC: 7317951. DOI: 10.1002/anie.202002768. View

Bohnenberger J, Feuerstein W, Himmel D, Daub M, Breher F, Krossing I . Stable salts of the hexacarbonyl chromium(I) cation and its pentacarbonyl-nitrosyl chromium(I) analogue. Nat Commun. 2019; 10(1):624. PMC: 6367395. DOI: 10.1038/s41467-019-08517-2. View

Chalkley M, Peters J . A Triad of Highly Reduced, Linear Iron Nitrosyl Complexes: {FeNO}(8-10). Angew Chem Int Ed Engl. 2016; 55(39):11995-8. PMC: 5079689. DOI: 10.1002/anie.201605403. View

10.

Morales-Cerrada R, Fliedel C, Daran J, Gayet F, Ladmiral V, Ameduri B . Fluoroalkyl Radical Generation by Homolytic Bond Dissociation in Pentacarbonylmanganese Derivatives. Chemistry. 2018; 25(1):296-308. DOI: 10.1002/chem.201804007. View

11.

Martens A, Weis P, Krummer M, Kreuzer M, Meierhofer A, Meier S . Facile and systematic access to the least-coordinating WCA [(RO)Al-F-Al(OR)] and its more Lewis-basic brother [F-Al(OR)] (R = C(CF)). Chem Sci. 2018; 9(35):7058-7068. PMC: 6137444. DOI: 10.1039/c8sc02591f. View

12.

Connelly N, Geiger W . Chemical Redox Agents for Organometallic Chemistry. Chem Rev. 1996; 96(2):877-910. DOI: 10.1021/cr940053x. View

13.

Distefano G . Photoionization Study of Fe(CO) and Ni(CO). J Res Natl Bur Stand A Phys Chem. 2020; 74A(2):233-239. PMC: 6701059. DOI: 10.6028/jres.074A.019. View

14.

Meier S, Himmel D, Krossing I . How does the Environment Influence a Given Cation? A Systematic Investigation of [Co(CO) ] in Gas Phase, Solution, and Solid State. Chemistry. 2018; 24(72):19348-19360. DOI: 10.1002/chem.201804546. View

15.

Bodenbinder M, Willner H, Batchelor R, Einstein F, Wang C, Aubke F . Syntheses and Vibrational and (13)C MAS-NMR Spectra of Bis(carbonyl)mercury(II) Undecafluorodiantimonate(V) ([Hg(CO)(2)][Sb(2)F(11)](2)) and of Bis(carbonyl)dimercury(I) Undecafluorodiantimonate ([Hg(2)(CO)(2)][Sb(2)F(11)](2)) and the Molecular.... Inorg Chem. 1996; 35(1):82-92. DOI: 10.1021/ic9507171. View

16.

Radtke V, Himmel D, Putz K, Goll S, Krossing I . The protoelectric potential map (PPM): an absolute two-dimensional chemical potential scale for a global understanding of chemistry. Chemistry. 2014; 20(15):4194-211. DOI: 10.1002/chem.201302473. View

17.

Bohnenberger J, Krossing I . Stable Salts of Heteroleptic Iron Carbonyl/Nitrosyl Cations. Angew Chem Int Ed Engl. 2019; 59(14):5581-5585. PMC: 7154531. DOI: 10.1002/anie.201915942. View

18.

Russell E, Cudjoe E, Mastromatteo M, Kercher J, Sztaray B, Bodi A . From iron pentacarbonyl to the iron ion by imaging photoelectron photoion coincidence. J Phys Chem A. 2013; 117(22):4556-63. DOI: 10.1021/jp402443e. View

19.

Bohnenberger J, Schmitt M, Feuerstein W, Krummenacher I, Butschke B, Czajka J . Completing the triad: synthesis and full characterization of homoleptic and heteroleptic carbonyl and nitrosyl complexes of the group VI metals. Chem Sci. 2021; 11(14):3592-3603. PMC: 8152671. DOI: 10.1039/c9sc06445a. View

20.

Keilwerth M, Hohenberger J, Heinemann F, Sutter J, Scheurer A, Fang H . A Series of Iron Nitrosyl Complexes {Fe-NO} and a Fleeting {Fe-NO} Intermediate en Route to a Metalacyclic Iron Nitrosoalkane. J Am Chem Soc. 2019; 141(43):17217-17235. DOI: 10.1021/jacs.9b08053. View