[μ-Bis(di-o-tolyl­phosphan­yl)methane-1:2κ2 P:P′]nona­carbonyl-1κ3 C,2κ3 C,3κ3 C-[tris­(2-chloro­eth­yl) phosphite-3κP]-triangulo-triruthenium(0)

Omar bin Shawkataly; Imthyaz Ahmed Khan; Siti Syaida Sirat; Ching Kheng Quah; Hoong-Kun Fun

doi:10.1107/S1600536812023707

. 2012 May 31;68(Pt 6):m838–m839. doi: 10.1107/S1600536812023707

[μ-Bis(di-o-tolylphosphanyl)methane-1:2κ² P:P′]nonacarbonyl-1κ³ C,2κ³ C,3κ³ C-[tris(2-chloroethyl) phosphite-3κP]-triangulo-triruthenium(0)

Omar bin Shawkataly ^a,^*,^‡, Imthyaz Ahmed Khan ^a,^§, Siti Syaida Sirat ^a,^¶, Ching Kheng Quah ^b,^‡‡, Hoong-Kun Fun ^b,^§§

PMCID: PMC3379179 PMID: 22719377

Abstract

In the title compound, [Ru₃(C₆H₁₂Cl₃O₃P)(C₂₉H₃₀P₂)(CO)₉], the bis(di-o-tolylphosphanyl)methane ligand bridges one Ru—Ru bond and the monodentate phosphite ligand bonds to the third Ru atom. Both ligands are equatorial with respect to the Ru₃ triangle. Each Ru atom bears one equatorial and two axial terminal carbonyl ligands. The dihedral angles between the two benzene rings in the diphenylphosphanyl groups are 79.52 (10) and 69.88 (10)°. In the crystal, molecules are linked via C—H⋯O hydrogen bonds into chains along [100].

Related literature

For general background to triangulo-triruthenium compounds with general structure Ru₃(CO)_12-n L _n (L = group 15 ligand) see: Bruce et al. (1985 ▶,1988a ▶,b ▶); Shawkataly et al. (1998 ▶, 2004 ▶, 2010 ▶, 2011 ▶). For the preparation of the di-o-tolylphosphanyl ligand, see: Filby et al. (2006 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶). graphic file with name e-68-0m838-scheme1.jpg

Experimental

Crystal data

[Ru₃(C₆H₁₂Cl₃O₃P)(C₂₉H₃₀P₂)(CO)₉]
M _r = 1265.25
Monoclinic,
a = 10.1705 (6) Å
b = 20.7490 (12) Å
c = 12.3584 (7) Å
β = 109.241 (1)°
V = 2462.3 (2) Å³
Z = 2
Mo Kα radiation
μ = 1.23 mm⁻¹
T = 100 K
0.63 × 0.30 × 0.09 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.513, T _max = 0.899
23611 measured reflections
11176 independent reflections
11085 reflections with I > 2σ(I)
R _int = 0.016

Refinement

R[F ² > 2σ(F ²)] = 0.016
wR(F ²) = 0.042
S = 1.05
11176 reflections
590 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.78 e Å⁻³
Δρ_min = −0.50 e Å⁻³
Absolute structure: Flack (1983 ▶), 5368 Friedel pairs
Flack parameter: 0.016 (10)

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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 datablock(s) global, I. DOI: 10.1107/S1600536812023707/rz2762sup1.cif

e-68-0m838-sup1.cif^{(55KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812023707/rz2762Isup2.hkl

e-68-0m838-Isup2.hkl^{(546.4KB, 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
C11—H11A⋯O1ⁱ	0.93	2.57	3.204 (3)	126

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors would like to thank the Malaysian Government and Universiti Sains Malaysia (USM) for the Research Grant Nos. 1001/PJJAUH/811188 and 1001/PFIZIK/811160. IAK is grateful to USM for a Visiting Researcher position, SSS thanks USM for a fellowship and CKQ thanks USM for an Incentive Grant.

supplementary crystallographic information

Comment

A large number of substituted derivatives of the type Ru₃(CO)_12-_nL_n (L = group 15 ligand) have been reported (Bruce et al.,1985, 1988a,b). As part of our study on the substitution of transition metal-carbonyl clusters with mixed-ligand complexes, we have published several structures of triangulo-triruthenium-carbonyl clusters containing mixed P/As and P/Sb ligands (Shawkataly et al., 1998, 2004, 2010, 2011). Herein we report the synthesis and structure of the title compound.

In the title triangulo-triruthenium compound, the bis(di-o-tolylphosphanyl)methane ligand bridges the Ru1–Ru2 bond and the monodentate phosphite ligand bonds to the Ru3 atom. Both phosphorous ligands are equatorial with respect to the Ru₃ triangle. Moreover, each Ru atom carries one equatorial and two axial terminal carbonyl ligands (Fig. 1). The dihedral angles between the two benzene rings (C1–C6/C7–C12 and C14–C19/C20–C25) are 79.52 (10) and 69.88 (10)° for the two diphenylphosphanyl groups respectively.

In the crystal structure, Fig. 2, molecules are linked via intermolecular C11–H11A···O1 hydrogen bonds (Table 1) into one-dimensional chains along [100].

Experimental

All manipulations were performed under a dry oxygen-free nitrogen atmosphere using standard Schlenk techniques. All solvents were dried over sodium and distilled from sodium benzophenone ketyl under dry oxygen free nitrogen. Tris(2-chloroethyl)phosphite (Aldrich) was used as received and bis(di-o-tolylphosphanyl)methane (Filby et al., 2006) was prepared by reported procedure. Ru₃(CO)₁₀(µ-(2-CH₃C₆H₄)₂PCH₂P(2-CH₃C₆H₄)₂) was prepared by reacting Ru₃(CO)₁₂ with bis(di-o-tolylphosphanyl)methane in presence of sodium benzophenone ketyl radical in THF (Shawkataly et al.,2011). The title compound was obtained by refluxing equimolar quantities of Ru₃(CO)₁₀(µ-(2-(CH₃C₆H₄)₂PCH₂P(2-CH₃C₆H₄)₂) and tris(2-chloroethyl)phosphite in hexane under nitrogen atmosphere. Crystals suitable for X-ray diffraction were grown by slow solvent/solvent diffusion of CH₃OH into CH₂Cl₂.