(η6-Benzene)­dichlorido­(chloro­dicyclo­hexyl­phosphane-κP)ruthenium(II) chloro­form monosolvate

Saravanan Gowrisankar; Helfried Neumann; Anke Spannenberg; Matthias Beller

doi:10.1107/S1600536814012975

. 2014 Jun 11;70(Pt 7):m255. doi: 10.1107/S1600536814012975

(η⁶-Benzene)dichlorido(chlorodicyclohexylphosphane-κP)ruthenium(II) chloroform monosolvate

Saravanan Gowrisankar ^a, Helfried Neumann ^b, Anke Spannenberg ^b, Matthias Beller ^b,^*

PMCID: PMC4120624 PMID: 25161521

Abstract

The title compound, [RuCl₂(η⁶-C₆H₆)(C₁₂H₂₂ClP)]·CHCl₃, was prepared by reaction of [RuCl₂(η⁶-C₆H₆)]₂ with chlorodicyclohexylphosphane in CHCl₃ at 323 K under argon. The Ru^II atom is surrounded by one arene ligand, two Cl atoms and a phosphane ligand in a piano-stool geometry. The phosphane ligand is linked by the P atom, with an Ru—P bond length of 2.3247 (4) Å. Both cyclohexyl rings at the P atom adopt a chair conformation. In the crystal, the Ru^II complex molecule and the chloroform solvent molecule are linked by a bifurcated C—H⋯(Cl,Cl) hydrogen bond. Intramolecular C—H⋯Cl hydrogen bonds are also observed.

Related literature

For the molecular structure of Ru complexes with the related chlorodiphenylphosphane ligand, see: Jantscher et al. (2009 ▶); Torres-Lubián et al. (1999 ▶). graphic file with name e-70-0m255-scheme1.jpg

Experimental

Crystal data

[RuCl₂(C₆H₆)(C₁₂H₂₂ClP)]·CHCl₃
M _r = 602.16
Monoclinic,
a = 7.9717 (1) Å
b = 16.3020 (2) Å
c = 18.0602 (3) Å
β = 91.244 (1)°
V = 2346.45 (6) Å³
Z = 4
Mo Kα radiation
μ = 1.42 mm⁻¹
T = 150 K
0.36 × 0.22 × 0.11 mm

Data collection

Bruker Kappa APEXII DUO diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.630, T _max = 0.859
37052 measured reflections
5619 independent reflections
4963 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.019
wR(F ²) = 0.048
S = 1.05
5619 reflections
244 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Data collection: APEX2 (Bruker, 2011 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, Global. DOI: 10.1107/S1600536814012975/is5363sup1.cif

e-70-0m255-sup1.cif^{(28.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814012975/is5363Isup2.hkl

e-70-0m255-Isup2.hkl^{(275.1KB, hkl)}

CCDC reference: 1006720

Additional supporting information: crystallographic information; 3D view; checkCIF report

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14B⋯Cl1	0.99	2.56	3.4080 (17)	144
C18—H18A⋯Cl1	0.99	2.74	3.5366 (17)	138
C19—H19⋯Cl1ⁱ	1.00	2.69	3.5539 (17)	144
C19—H19⋯Cl2ⁱ	1.00	2.77	3.6119 (18)	142

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Symmetry code: (i) Inline graphic .

supplementary crystallographic information

S1. Comment

The half-sandwich (η⁶–C₆H₆)-dichlorido(chlorodicyclohexylphosphane)ruthenium(II) complex was formed by reaction of one equivalent of [RuCl₂(η⁶-C₆H₆)]₂ with two equivalents of (Cy₂P(1-naphthoyl)) ligand under hydrogenation conditions (CHCl₃, 60 bar of H₂, 353 K, 3 hrs) as a side product. The cleavage of the 1-naphthoyl group from [RuCl₂(η⁶-C₆H₆)(Cy₂P(1-naphthoyl)] complex forms firstly [RuCl₂(η⁶-C₆H₆)(Cy₂PH)] and subsequent chlorination of the dicyclohexylphosphane unit due to CHCl₃ yields the title compound in poor yield. Additionally, we could not observe any trace amount of title compound by using non-chlorinated solvents such as MeOH. The substitution of hydrogen next to phosphane by chlorine coming from solvent molecules is also described for the formation of a Ru-complex with the related chlorodiphenylphosphane ligand by Torres-Lubián et al. (1999). More specifically, the title complex was formed by reaction of [RuCl₂(η⁶-C₆H₆)]₂ with chlorodicyclohexylphosphane in CHCl₃ at 323 K under argon in 41% yield. Crystals suitable for X-ray crystal structure analysis could be obtained by crystallization from a chloroform/heptane mixture. In the ³¹P NMR spectrum of the complex the signal for the phosphorus was observed at 156.3 p.p.m., whereas free ligand signal appears at 128.8 p.p.m.. The title compound shows the three legged piano-stool geometry at the ruthenium centre with the arene, chlorodicyclohexylphosphane and two chlorine ligands in the coordination sphere (Fig. 1). The phosphane ligand is linked by the phosphorus with a Ru—P bond length of 2.3247 (4) Å. Both cyclohexyl rings at the phosphorus atom adopt a chair conformation. The Ru complex is co-crystallized with CHCl₃.

S2. Experimental

A 50 ml round bottom flask with inert gas valve was charged with 0.05 mmol (25 mg) [RuCl₂(η⁶-C₆H₆)]₂ and 4 ml CHCl₃ under argon atmosphere. To this suspension 0.105 mmol (21 µL) chlorodicyclohexylphosphane was added and the reaction mixture was allowed to react 3 h at 323 K. A clear red brown solution has been formed and the volume was reduced carefully in high vacuum to ca 1 ml. Next 20 ml heptane was added to the reaction mixture and cooled for 1 h with ice bath. The precipitate was washed with heptane (3 × 5 ml) to yield the title compound as an orange brown solid (20 mg, 41%). Red single crystals were grown in CHCl₃/heptane mixture at 245 K for 1 day. ¹H NMR (300 MHz), CDCl₃): δ 5.71 (s, 6H, benzene), 2.79 (m, 2H, Cy), 2.06–1.54 (m, 14H, Cy), 1.27 (br s, 6H, Cy). ¹³C {¹H} NMR (75 MHz, CDCl₃): δ 89.8 (RuPh), 40.4 (d, J_PC = 9.5 Hz, PCH), 27.2, 26.9, 26.7, 26.4, 26.3, 26.0, 26.0, 25.6 (CH₂). ³¹P {¹H} NMR (121 MHz, CDCl₃): δ 156.3.