Penta­carbonyl-1κ2 C,2κ3 C-[(diphenyl­phosphor­yl)diphenyl­phosphane-1κP]-μ-ethane-1,2-dithiol­ato-1:2κ4 S,S′:S,S′-diiron(I)(Fe—Fe)

Xu-Feng Liu; Xiao-Yong Yu

doi:10.1107/S1600536811042139

. 2011 Oct 22;67(Pt 11):m1552. doi: 10.1107/S1600536811042139

Pentacarbonyl-1κ² C,2κ³ C-[(diphenylphosphoryl)diphenylphosphane-1κP]-μ-ethane-1,2-dithiolato-1:2κ⁴ S,S′:S,S′-diiron(I)(Fe—Fe)

Xu-Feng Liu ^a,^*, Xiao-Yong Yu ^a

PMCID: PMC3246973 PMID: 22219793

Abstract

The dinuclear title compound, [Fe₂(C₂H₄S₂)(C₂₄H₂₀OP₂)(CO)₅] or (μ-SCH₂CH₂S-μ)Fe₂(CO)₅[Ph₂PP(O)Ph₂], contains a butterfly-shaped Fe₂S₂ core in which the Fe⋯Fe separation is 2.5275 (6) Å. One of the Fe atoms is also coordinated to three carbonyl ligands and the other to two carbonyl ligands and one phosphane ligand [Ph₂PP(O)Ph₂]. Both Fe-atom geometries could be described as grossly distorted octahedral and the Ph₂PP(O)Ph₂ ligand lies trans to the Fe⋯Fe link.

Related literature

For more details about diiron dithiolate complexes, see: Song et al. (2005 ▶); Wang et al. (2009 ▶); Yin et al. (2011 ▶).

Experimental

Crystal data

[Fe₂(C₂H₄S₂)(C₂₄H₂₀OP₂)(CO)₅]
M _r = 730.26
Monoclinic,
a = 13.865 (4) Å
b = 15.398 (4) Å
c = 14.459 (5) Å
β = 98.357 (4)°
V = 3054.1 (16) Å³
Z = 4
Mo Kα radiation
μ = 1.24 mm⁻¹
T = 113 K
0.20 × 0.18 × 0.10 mm

Data collection

Rigaku Saturn724 CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ▶) T _min = 0.790, T _max = 0.886
31351 measured reflections
7281 independent reflections
6102 reflections with I > 2σ(I)
R _int = 0.039

Refinement

R[F ² > 2σ(F ²)] = 0.026
wR(F ²) = 0.059
S = 1.06
7281 reflections
388 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2005 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811042139/hb6442sup1.cif

e-67-m1552-sup1.cif^{(28.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811042139/hb6442Isup2.hkl

e-67-m1552-Isup2.hkl^{(356.3KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Fe1—C2	1.7855 (18)
Fe1—C1	1.7981 (17)
Fe1—C3	1.8006 (18)
Fe1—S1	2.2484 (6)
Fe1—S2	2.2495 (8)
Fe2—C4	1.7733 (17)
Fe2—C5	1.7742 (17)
Fe2—P1	2.2426 (7)
Fe2—S1	2.2495 (7)
Fe2—S2	2.2530 (7)

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Acknowledgments

This work was supported by the Ningbo petrochemical application-oriented base projects (Jd080109 and Jd090110).

supplementary crystallographic information

Comment

Diiron dithiolate complexes have received much attention in recent years due to their structures close to the active site of [FeFe]-hydrogenases (Song et al. (2005), Wang et al. (2009), Yin et al. (2011)). In continuation of our work in this area, the title complex, (I), was synthesized and its strucuture was determined by X-ray crstallography.

As shown in Fig. 1, the title complex contains five carbonyls and one Ph₂PP(O)Ph₂ ligands. The diiron ethanedithiolate cluster consists of two fused five-membered rings. The Ph₂PP(O)Ph₂ ligands occupies an axial position of the square-pyramidal geometry of the Fe atom.

Experimental

The title complex was prepared from (µ-SCH₂CH₂S-µ)Fe₂(CO)₆ and 1,2-bis(diphenylphosphino)cyclopentane in the presence of Me₃NO. Colourless prisms were grown from slow evaporation of dichloromethane and hexane solution at room temperature.