A Caged Neutral 17-Valence-Electron Iron(I) Radical [Fe(CO)2(Cl)(P((CH2)10)3P)]•: Synthetic, Structural, Spectroscopic, Redox, and Computational Studies

Zarcone SR, Zhang Z, Handunneththige S, Ni Z, Bhuvanesh N, Nippe M, Meyer K, Hall MB, Gladysz JA (2024)


Publication Type: Journal article

Publication year: 2024

Journal

DOI: 10.1021/acs.inorgchem.4c02275

Abstract

UV irradiation of yellow CH2Cl2 solutions of trans-Fe(CO)3(P((CH2)10)3P) (2a) and PMe3 (10 equiv) gives, in addition to the previously reported dibridgehead diphosphine P((CH2)10)3P (46%), a green paramagnetic complex that crystallography shows to be the trigonal-bipyramidal iron(I) radical trans-[Fe(CO)2(Cl)(P((CH2)10)3P)] (1a; 31% after workup). This is a rare example of an isolable species of the formula [Fe(CO)4-n(L)n(X)] (n = 0-3, L = two-electron-donor ligand; X = one-electron-donor ligand). Analogous precursors with longer P(CH2)nP segments (n = 12, 14, 16, 18) give only the demetalated diphosphines, and a rationale is proposed. The magnetic susceptibility of 1a, assayed by Evans’ method and SQUID measurements, indicates a spin (S) of 1/2. Cyclic voltammetry shows that 1a undergoes a partially reversible one-electron oxidation, but no facile reduction. The UV-visible, EPR, and 57Fe Mössbauer spectra are analyzed in detail. Complex 2a is similarly studied, and, despite the extra valence electron, exhibits a comparable oxidation potential (ΔE1/2 ≤ 0.04 V). The crystal structure shows a cage conformation, solvation level, disorder motif, and unit cell parameters essentially identical to those of 1a. DFT calculations provide much insight regarding the structural, redox, and spectroscopic properties.

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APA:

Zarcone, S.R., Zhang, Z., Handunneththige, S., Ni, Z., Bhuvanesh, N., Nippe, M.,... Gladysz, J.A. (2024). A Caged Neutral 17-Valence-Electron Iron(I) Radical [Fe(CO)2(Cl)(P((CH2)10)3P)]•: Synthetic, Structural, Spectroscopic, Redox, and Computational Studies. Inorganic Chemistry. https://doi.org/10.1021/acs.inorgchem.4c02275

MLA:

Zarcone, Samuel R., et al. "A Caged Neutral 17-Valence-Electron Iron(I) Radical [Fe(CO)2(Cl)(P((CH2)10)3P)]•: Synthetic, Structural, Spectroscopic, Redox, and Computational Studies." Inorganic Chemistry (2024).

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