[μ-Bis­(diphenyl­phosphino)methane-1:2κ2 P:P′]nonacarbonyl-1κ3 C,2κ3 C,3κ3 C-[tris­(4-methyl­phen­yl)arsine-3κAs]-triangulo-triruthenium(0)

Omar bin Shawkataly; Imthyaz Ahmed Khan; Chin Sing Yeap; Hoong-Kun Fun

doi:10.1107/S1600536809046704

. 2009 Nov 21;65(Pt 12):m1622–m1623. doi: 10.1107/S1600536809046704

[μ-Bis(diphenylphosphino)methane-1:2κ² P:P′]nonacarbonyl-1κ³ C,2κ³ C,3κ³ C-[tris(4-methylphenyl)arsine-3κAs]-triangulo-triruthenium(0)

Omar bin Shawkataly ^a,^*,^‡, Imthyaz Ahmed Khan ^a, Chin Sing Yeap ^b,^§, Hoong-Kun Fun ^b,^¶

PMCID: PMC2972049 PMID: 21578644

Abstract

In the title triangulo-triruthenium compound, [Ru₃(C₂₁H₂₁As)(C₂₅H₂₂P₂)(CO)₉], the bis(diphenylphosphino)methane ligand bridges an Ru—Ru bond and the monodentate arsine ligand bonds to the third Ru atom. Both the phosphine and arsine ligands are equatorial with respect to the Ru₃ triangle. Additionally, each Ru atom carries one equatorial and two axial terminal carbonyl ligands. The three arsine-substituted phenyl rings make dihedral angles of 87.36 (10), 81.96 (10) and 73.37 (11)° with each other. The dihedral angles between the two phenyl rings are 88.08 (12) and 80.15 (10)° for the two diphenylphosphino groups. In the crystal packing, the molecules are linked together as dimers via intermolecular C—H⋯O hydrogen bonds. These dimers are stacked down b axis. Intermolecular C—H⋯π and π–π interactions [centroid–centroid distance = 3.6383 (13) Å] further stabilize the crystal structure.

Related literature

For general background to triangulo-triruthenium derivatives, see: Bruce et al. (1985 ▶, 1988a ▶, 1988b ▶); Shawkataly et al. (1998 ▶, 2009a ▶). For related structures, see: Shawkataly et al. (2006 ▶, 2009a ▶,b ▶,c ▶). For the synthesis of bis(diphenylphosphino)methane, see: Bruce et al. (1983 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶). graphic file with name e-65-m1622-scheme1.jpg

Experimental

Crystal data

[Ru₃(C₂₁H₂₁As)(C₂₅H₂₂P₂)(CO)₉]
M _r = 1287.96
Triclinic,
a = 11.1241 (1) Å
b = 12.1660 (2) Å
c = 20.0895 (3) Å
α = 91.406 (1)°
β = 101.116 (1)°
γ = 102.473 (1)°
V = 2598.63 (6) Å³
Z = 2
Mo Kα radiation
μ = 1.61 mm⁻¹
T = 100 K
0.29 × 0.22 × 0.06 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.653, T _max = 0.907
104298 measured reflections
24677 independent reflections
19683 reflections with I > 2σ(I)
R _int = 0.035

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.084
S = 1.02
24677 reflections
634 parameters
H-atom parameters constrained
Δρ_max = 3.41 e Å⁻³
Δρ_min = −1.34 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); 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/S1600536809046704/sj2670sup1.cif

e-65-m1622-sup1.cif^{(42.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809046704/sj2670Isup2.hkl

e-65-m1622-Isup2.hkl^{(1.2MB, 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
C16—H16A⋯O3ⁱ	0.93	2.49	3.377 (3)	159
C3—H3A⋯Cg1ⁱⁱ	0.93	2.93	3.708 (3)	142
C22—H22A⋯Cg2ⁱⁱⁱ	0.93	2.78	3.453 (2)	130
C53—H53B⋯Cg3^iv	0.96	2.94	3.801 (3)	150

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) . Cg1, Cg2 and Cg3 are centroids of the C20–C25 phenyl ring and C26–C32 and C38–C43 benzene rings, respectively.

Acknowledgments

The authors would like to thank the Malaysian Government and Universiti Sains Malaysia (USM) for the Research grant 1001/PJJAUH/811115. IAK is grateful to USM for a Postdoctoral Fellowship and Gokhale Centenary College, Ankola, Karnataka, India, for study leave. HKF thanks USM for the Research University Golden Goose grant 1001/PFIZIK/811012. CSY thanks USM for the award of a USM Fellowship.

supplementary crystallographic information

Comment

Tri-angulotriruthenium clusters are known for their interesting structural variations and related catalytic activity. A large number of substituted derivatives, Ru₃(CO)_12-nL_n (L=15 group ligand) have been reported (Bruce et al., 1988a,b; Bruce et al., 1985). In continuation of our interest in the substituted clusters (Shawkataly et al., 1998, 2009a) we report here the synthesis and structure of Ru₃(CO)₉(µ-Ph₂PCH₂PPh₂)(As(4-CH₃C₆H₄)₃).

The bond lengths and angles of title compound (Fig. 1) are comparable to those in related structures (Shawkataly et al., 2006, 2009a,b,c). The bis(diphenylphosphino)methane ligand bridges the Ru1—Ru2 bond and the monodentate arsine ligand bonds to the Ru3 atom. Both the phosphine and arsine ligands are equatorial with respect to the Ru₃ triangle. Additionally, each Ru atom carries one equatorial and two axial terminal carbonyl ligands. The three arsine substituted phenyl rings make dihedral angles (C26–C31/C32–C37, C26–C31/C38–C43 and C32–C37/C38–C43) of 87.36 (10), 81.96 (10) and 73.37 (11)° with each other respectively. The dihedral angles between the two phenyl rings (C1–C6/C7–C12 and C14–C19/C20–C25) are 88.08 (12) and 80.15 (10)° for the two diphenylphosphino groups respectively.

In the crystal packing (Fig. 2), the molecules are linked together as dimers via intermolecular C—H···O hydrogen bonds. These dimers are stacked down b axis. Intermolecular C—H···π (Table 1) and π–π interactions further stabilize the crystal structure with Cg4···Cg4 = 3.6383 (13) Å, -1 - x, -y, 1 - z (Cg4 is centroid of phenyl ring C14–C19).

Experimental

Reactions were conducted under an atmosphere of nitrogen using standard Schlenk techniques and hexane-dried over sodium metal. Tris(4-methylphenyl)arsine (Maybridge) is used as received and bis(diphenylphosphino)methane (Bruce et al., 1983) was prepared by a reported procedure. Ru₃(CO)₁₀(µ-Ph₂PCH₂PPh₂) (102.4 mg, 0.1 mmol) and tris(p-tolyl)arsine (34.83 mg, 0.1 mmol) were refluxed for 15 minutes in hexane (25 ml) under a current of nitrogen. The reaction mixture turned intense red. The solvent was removed under vacuum. The reaction mixture was separated by TLC (dichloromethane:hexane, 30:70). Two bands appeared. The major band (red) R_f = 0.56 yielded the title compound which was crystallized from CH₂Cl₂ - CH₃OH, yield = 60 mg, 43.73%, m.p. 197–200 °C. IR(cyclohexane).ν(CO) 2082 s, 2000 s, 1981 s, cm^-1. ¹H NMR (CDCl₃), δ 7.144–7.499 (32H, Ph), δ 4.185–4.336 (m, 2H, –CH₂–), δ 2.365 (s, 9H, 3CH₃).