Undeca­carbonyl-1κ3 C,2κ4 C,3κ4 C-[tris­(2-chloro­eth­yl) phosphite-1κP]-triangulo-triruthenium(0)

Omar bin Shawkataly; Syed Sauban Ghani; Rajabathar Jothiramalingam; Chin Sing Yeap; Hoong-Kun Fun

doi:10.1107/S1600536810033891

. 2010 Sep 4;66(Pt 10):m1191–m1192. doi: 10.1107/S1600536810033891

Undecacarbonyl-1κ³ C,2κ⁴ C,3κ⁴ C-[tris(2-chloroethyl) phosphite-1κP]-triangulo-triruthenium(0)

Omar bin Shawkataly ^a,^*,^‡, Syed Sauban Ghani ^a, Rajabathar Jothiramalingam ^a, Chin Sing Yeap ^b,^§, Hoong-Kun Fun ^b,^¶

PMCID: PMC2983316 PMID: 21587355

Abstract

In the title triangulo-triruthenium compound, [Ru₃(C₆H₁₂Cl₃O₃P)(CO)₁₁], one equatorial carbonyl ligand is substituted by a monodentate phosphite ligand, leaving one equatorial and two axial carbonyl ligands on one Ru atom. The remaining two Ru atoms each carry two equatorial and two axial terminal carbonyl ligands. In the crystal structure, the molecules are linked into a one-dimensional column along [100] by intermolecular C—H⋯O hydrogen bonds.

Related literature

For general background to triangulo-triruthenium derivatives, see: Bruce et al. (1985 ▶, 1988a ▶,b ▶). For the synthesis, see: Bruce et al. (1987 ▶). For related structures, see: Shawkataly et al. (1991 ▶, 2010 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

[Ru₃(C₆H₁₂Cl₃O₃P)(CO)₁₁]
M _r = 880.80
Triclinic,
a = 7.8592 (9) Å
b = 12.5979 (14) Å
c = 14.8393 (17) Å
α = 109.442 (3)°
β = 93.791 (3)°
γ = 90.763 (3)°
V = 1381.4 (3) Å³
Z = 2
Mo Kα radiation
μ = 2.03 mm⁻¹
T = 100 K
0.20 × 0.19 × 0.03 mm

Data collection

Bruker APEXII DUO CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.691, T _max = 0.936
32458 measured reflections
11981 independent reflections
9935 reflections with I > 2σ(I)
R _int = 0.037

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.120
S = 1.07
11981 reflections
343 parameters
H-atom parameters constrained
Δρ_max = 1.36 e Å⁻³
Δρ_min = −1.36 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810033891/hy2343sup1.cif

e-66-m1191-sup1.cif^{(24.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810033891/hy2343Isup2.hkl

e-66-m1191-Isup2.hkl^{(585.7KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C17—H17B⋯O4ⁱ	0.97	2.58	3.297 (4)	131
C17—H17B⋯O5ⁱⁱ	0.97	2.54	3.307 (4)	136

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

Acknowledgments

The authors gratefully acknowledge funding from the Malaysian Government and Universiti Sains Malaysia (USM) under the University Research Grant 1001/PJJAUH/811115. SSG thanks USM for a post-doctoral fellowship. HKF and CSY thank USM for the Research University Golden Goose Grant 1001/PFIZIK/811012 and CSY also thanks USM for the award of a USM Fellowship.

supplementary crystallographic information

Comment

Syntheses and structures of substituted triangulo-triruthenium clusters have been of interest to researchers due to observed structural variations and their potential catalytic activity. A large number of substituted derivatives, Ru₃(CO)_12-nL_n (L= group 15 ligands), have been reported (Bruce et al., 1985, 1988a,b). As part of our ongoing studies on phosphite substituted triangulo-triruthenium clusters (Shawkataly et al., 1991, 2010), herein we report the structure of the title compound.

In the title compound (Fig. 1), a monodentate phosphite ligand has replaced a single carbonyl ligand of the Ru₃ triangle. The monodentate phosphite ligand is bonded equatorially to the Ru1 atoms of the triangulo-triruthenium unit. Thus, the Ru2 and Ru3 atoms each carry two equatorial and two axial terminal carbonyl ligands, while the phosphite-bonded Ru1 atom binds one equatorial and two axial terminal carbonyl ligands.

In the crystal structure, the molecules are linked into a one-dimensional column along [1 0 0] by intermolecular C—H···O hydrogen bonds (Fig. 2, Table 1).

Experimental

All the manipulations were performed under a dry oxygen-free nitrogen atmosphere using standard Schlenk techniques. THF was dried over sodium wire and freshly distilled from sodium benzophenone ketyl solution. The title compound was prepared by mixing Ru₃(CO)₁₂ (Aldrich) and P(OCH₂CH₂Cl)₃ (Maybridge) in a 1:1 molar ratio in THF at 40°C. Diphenylketyl radical anion initiator of about 0.2 ml (synthesized as per the method of Bruce et al., 1987) was introduced into the reaction mixture under a current of nitrogen. After stirring of 15 min, the solvent was removed under vacuum. Separation of the product in a pure form was done by column chromatography (Florisil, 100–200 mesh; eluant, dichloromethane: hexane). Crystals suitable for X-ray diffraction were grown by slow diffusion of CH₃OH into the CH₂Cl₂ solution.