trans-Di-μ-carbonyl-bis­{carbon­yl[η5-2,3,4,5-tetra­methyl-1-(2-thien­yl)cyclo­penta­dien­yl]ruthenium(I)}(Ru—Ru)

Zhi-Hong Ma; Gui-Ying Dong; Xiao-Huan Liu; Jin Lin

doi:10.1107/S1600536809026063

. 2009 Jul 11;65(Pt 8):m894. doi: 10.1107/S1600536809026063

trans-Di-μ-carbonyl-bis{carbonyl[η⁵-2,3,4,5-tetramethyl-1-(2-thienyl)cyclopentadienyl]ruthenium(I)}(Ru—Ru)

Zhi-Hong Ma ^a,^b, Gui-Ying Dong ^c, Xiao-Huan Liu ^a, Jin Lin ^a,^*

PMCID: PMC2977155 PMID: 21583356

Abstract

The title compound, [Ru₂(C₁₃H₁₅S)₂(CO)₄], is a centrosymmetric binuclear metal–carbonyl complex containing an Ru—Ru single bond [2.7511 (8) Å]. Each Ru^I atom is coordinated by two bridging carbonyl ligands, one terminal carbonyl ligand and one η⁵-cyclopentadienyl group. The complex has a trans conformation and the two cyclopentadienyl ring planes are parallel. The crystal structure involves weak C—H⋯O hydrogen bonds.

Related literature

For general background to substituted cyclopentadienyl–metal complexes, see: Arndt (2002 ▶); Bailey et al. (1978 ▶); King (1976 ▶); Möhring & Coville (2006 ▶). For the crystal structures of related ruthenium complexes, see: Schumann et al. (2002 ▶).

Experimental

Crystal data

[Ru₂(C₁₃H₁₅S)₂(CO)₄]
M _r = 720.82
Triclinic,
a = 8.269 (2) Å
b = 8.899 (3) Å
c = 10.056 (3) Å
α = 81.826 (4)°
β = 76.083 (5)°
γ = 82.876 (5)°
V = 707.9 (4) Å³
Z = 1
Mo Kα radiation
μ = 1.25 mm⁻¹
T = 273 K
0.15 × 0.12 × 0.10 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.835, T _max = 0.885
3667 measured reflections
2493 independent reflections
2431 reflections with I > 2σ(I)
R _int = 0.016

Refinement

R[F ² > 2σ(F ²)] = 0.027
wR(F ²) = 0.100
S = 1.03
2493 reflections
173 parameters
H-atom parameters constrained
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.63 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; 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: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809026063/hy2205sup1.cif

e-65-0m894-sup1.cif^{(24KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809026063/hy2205Isup2.hkl

e-65-0m894-Isup2.hkl^{(122.5KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Ru1—C1	2.018 (3)
Ru1—C1ⁱ	2.048 (3)
Ru1—C2	1.862 (3)
Ru1—C3	2.246 (3)
Ru1—C4	2.291 (3)
Ru1—C5	2.302 (3)
Ru1—C6	2.282 (3)
Ru1—C7	2.217 (3)

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Symmetry code: (i) Inline graphic .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯O2ⁱⁱ	0.93	2.60	3.335 (5)	136
C14—H14B⋯O2ⁱ	0.96	2.58	3.319 (4)	134

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

This work was supported financially by the Hebei Natural Science Foundation of China (No. B2008000150) and the Research Fund for the Doctoral Program of Hebei Normal University (No. L2005B18).

supplementary crystallographic information

Comment

Cyclopentadienyl metal complexes have been extensively investigated since ferrocene has been discovered. Replacement of the hydrogen atoms by other substituents alters both the steric and electronic influences of the H⁵-cyclopentadienyl ring, resulting in differing reactivity and stability of the substituted cyclopentadienyl metal complexes (Arndt, 2002; King, 1976). Especially for metallocene polymerization catalysts, the steric and electronic effects of the substituents on cyclopentadienyl ring greatly influence catalytic activity (Bailey et al., 1978; Möhring & Coville, 2006).

The title compound, [Ru₂(C₁₃H₁₅S)₂(CO)₄], is a centrosymmetric binuclear metal–carbonyl complex containing an Ru—Ru single bond. As shown in Fig. 1, the cyclopentadienyl ring of the organic ligand coordinates to the Ru^I atom (Table 1), while the thienyl group acting as a substituent is uncoordinated. The Ru1—Cg1 distance is 1.911 (3) Å, where Cg1 is the centroid of the cyclopentadienyl ring. The Ru—Ru bond distance is 2.7511 (8) Å and agrees with that observed in the analogous structure [2.751 (1) Å] (Schumann et al., 2002). The two cyclopentadienyl rings are parallel by virtue of the center of symmetry. The complex has a trans conformation, with two bridging carbonyl ligands and two terminal carbonyl ligands. The crystal packing is stabilized by weak C—H···O hydrogen bonds (Table 2).

Experimental

A solution of 1-(2-thienyl)-2,3,4,5-tetramethylcyclopentadiene (0.288 g, 1.41 mmol) and Ru₃(CO)₁₂ (0.30 g, 0.47 mmol) in xylene (30 ml) was refluxed for 12 h. The solvent was removed under vacuum and the residue was chromatographed on an Al₂O₃ column using petroleum ether/dichloromethane (volume ratio = 1:3) as eluent. The red band was collected, and after several days red crystals were obtained (yield 0.142 g, 27.9%). Analysis calculated for C₃₀H₃₀O₄Ru₂S₂: C 49.99, H 4.19%; found: C 49.94, H 4.21%.