(18-Crown-6)potassium [(1,2,5,6-η)-cyclo­octa-1,5-diene][(1,2,3,4-η)-naph­tha­lene]­ferrate(−I)

William W Brennessel; John E Ellis

doi:10.1107/S160053681203704X

. 2012 Sep 1;68(Pt 10):m1230–m1231. doi: 10.1107/S160053681203704X

(18-Crown-6)potassium [(1,2,5,6-η)-cycloocta-1,5-diene][(1,2,3,4-η)-naphthalene]ferrate(−I)

William W Brennessel ^a,^*, John E Ellis ^a

PMCID: PMC3470125 PMID: 23125569

Abstract

The title salt, [K(C₁₂H₂₄O₆)][Fe(C₈H₁₂)(C₁₀H₈)], is the only known naphthalene complex containing iron in a formally negative oxidation state. Each (naphthalene)(1,5-cod)ferrate(−I) anion is in contact with one (18-crown-6)potassium cation via K⋯C contacts to the outer four carbon atoms of the naphthalene ligand (cod = 1,5-cyclooctadiene, 18-crown-6 = 1,4,7,10,13,16-hexaoxacyclooctadecane). When using the midpoints of the coordinating olefin bonds, the overall geometry of the coordination sphere around iron can be best described as distorted tetrahedral. The naphthalene fold angle between the plane of the iron-coordinating butadiene unit and the plane containing the exo-benzene moiety is 19.2 (1)°.

Related literature

For the known complexes that contain iron in a formally negative oxidation state with solely olefinic ligands, see: Jonas (1979 ▶, 1981 ▶); Jonas et al. (1979 ▶); Jonas & Krüger (1980 ▶); Brennessel et al. (2007 ▶). For the various syntheses of the cobalt analog of the title complex, see: Brennessel et al. (2006 ▶); Brennessel & Ellis (2012 ▶). For an example of a diamagnetic, formally Fe(0) naphthaleneferrate(−I), see: Schnökelborg et al. (2012 ▶). For details of the preparation and purification of reagents and solvents, and for descriptions of the equipment and techniques, see: Brennessel (2009 ▶). For a discussion of polyaromatic hydrocarbons and their Dewar’s resonance energies, see: Milun et al. (1972 ▶).

Experimental

Crystal data

[K(C₁₂H₂₄O₆)][Fe(C₈H₁₂)(C₁₀H₈)]
M _r = 595.60
Triclinic,
a = 9.244 (1) Å
b = 10.5285 (12) Å
c = 15.971 (2) Å
α = 76.085 (2)°
β = 89.651 (2)°
γ = 74.949 (2)°
V = 1454.4 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.70 mm⁻¹
T = 173 K
0.42 × 0.32 × 0.22 mm

Data collection

Siemens SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a ▶) T _min = 0.666, T _max = 0.746
17413 measured reflections
6610 independent reflections
5576 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.073
S = 1.04
6610 reflections
423 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: SMART (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b ▶); molecular graphics: SHELXTL (Sheldrick, 2008b ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681203704X/wm2674sup1.cif

e-68-m1230-sup1.cif^{(49.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681203704X/wm2674Isup2.hkl

e-68-m1230-Isup2.hkl^{(323.5KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This research was supported by the US National Science Foundation and the donors of the Petroleum Research Fund, administered by the American Chemical Society.

supplementary crystallographic information

Comment

To date there are very few reported complexes of iron in a formally negative oxidation state and supported solely by olefinic ligands. In the 1970s Klaus Jonas and coworkers devised a way to synthesize (L)₂Li₂Fe(C═C)₂, where L = tetramethylethylenediamine and C═C = 2(ethylene) or 1,5-cyclooctadiene (cod) or L = 1,2-dimethoxyethane (dme) and C═C = 1,5-cod (Jonas, 1979, 1981; Jonas et al., 1979; Jonas & Krüger, 1980), for which the cod complex is a direct derivative of the ethylene complex. Because ferrocene (FeCp₂) was the starting material, the synthesis of the homoleptic ethylene complex required pressurized ethylene gas to fully displace both cyclopentadienyl ligands (5 atm prior to heating to 323 K in a closed vessel; Jonas, 1979). To avoid the need for the superambient pressures necessary with ferrocene, we devised syntheses from a ferrous halide, FeBr₂. Recently we reported the syntheses of new ferrate anions bis(anthracene)ferrate(-I), bis(butadiene)ferrate(-I), and mixed-ligand (anthracene)(1,5-cod)ferrate(-I) (Brennessel et al., 2007). The title complex is unique because it is the sole example of a naphthalene complex containing iron in a formally negative oxidation state. Only one other naphthaleneferrate(-I) has been reported in the primary literature, a diamagnetic formally Fe(0) complex, (18-crown-6)potassium (η⁵-C₅Me₅)(η⁴-naphthalene)ferrate(-I) (Schnökelborg et al., 2012). Several neutral and cationic heteroleptic naphthalene—iron complexes have also been structurally characterized, as discussed elsewhere (Brennessel, 2009).

Unlike what was observed in the cobalt system, in which the reduction of CoBr₂ by three equivalents of potassium naphthalene in the presence of excess 1,5-cod led to the homoleptic 1,5-cod anion [Co(η⁴-1,5-cod)₂]^- (Brennessel et al., 2006; Brennessel & Ellis, 2012), only one molecule of 1,5-cod is found coordinating to the iron atom regardless of excess 1,5-cod. This was not the only product, since carbonylation of the bulk material showed ν_CO stretching frequencies corresponding to [Fe₂(CO)₈]^2- (major) and [Fe(CO)₄]^2- (minor). If the naphthalene radical anion is reducing enough to afford an Fe(-II) species directly, then that species could be the precursor to the minor carbonylation product, the Fe(-II) carbonyl. However, since the yield of the title complex is modest (40–50%), there is likely excess reducing agent left over from the initial reduction which easily could have reduced the Fe(-I) carbonyl to Fe(-II). Unfortunately, it has proved very difficult to separate the title complex from the naphthalene radical anion, and no further optimizations or characterizations have been performed to date.

The bond lengths of the metal-coordinating olefins (C1═C2 and C3═C4, Figure 1) of the naphthalene ligand (1.424 (3) Å, avg.) are statistically identical to those found in the related anthracene-cod ferrate anion, [Fe(C₁₄H₁₀)(C₈H₁₂)]^- (1.422 (4) Å, avg.; Brennessel et al., 2007), which suggests that naphthalene is performing an equivalent role in supporting the low-valent iron atom. Even so, anthracene quantitatively displaces naphthalene at room temperature in THF solution (i.e., the title complex can be converted to the anthracene-cod ferrate with ease), a result that can be justified with Dewar's resonance energies (Milun et al., 1972). Both the title complex and the anthracene-cod ferrate have an essentially tetrahedral geometry about their iron atoms and have similar polyaromatic hydrocarbon fold angles (for the title structure the fold angle between the planes defined by atoms C1, C2, C3, C4 and C1, C4, C5, C6, C7, C8, C9, C10, respectively, amounts to 19.2 (1) °.)

The packing of the molecular entities is shown in Figure 2.

Experimental

Details on the preparation and purification of reagents and solvents, and descriptions of the equipment and techniques can be found elsewhere (Brennessel, 2009). Under argon, an orange slurry of anhydrous FeBr₂ (0.500 g, 2.32 mmol) in THF (50 ml, 195 K) was added to a deep green solution of K[C₁₀H₈] (6.86 mmol) and excess 1,5-cyclooctadiene (0.882 g, 8.15 mmol) in THF (50 ml, 195 K). The resulting reddish-yellow solution was warmed slowly to room temperature, when it was filtered to remove KBr. 18-crown-6 (0.613 g, 2.32 mmol) in THF (30 ml) was added to the deep red filtrate and the solvent was removed in vacuo. Pentane (40 ml) was added and the solid was carefully scraped off the flask wall with the stir bar. The slurry was then filtered, and the product was washed with pentane (30 ml) and dried in vacuo, yielding a dark red solid (0.607 g, 44% assuming the uni-negative title complex: see Comment above). An analytically pure bulk sample has not been obtained to date. Dark red blocks were grown from a pentane-layered THF solution at 273 K.