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

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.