trans-Carbonyl­chloridobis[diphen­yl(4-vinyl­phen­yl)phosphane-κP]rhodium(I)

Hezron Ogutu; Leo Kirsten; Reinout Meijboom

doi:10.1107/S1600536812013669

. 2012 Apr 4;68(Pt 5):m545. doi: 10.1107/S1600536812013669

trans-Carbonylchloridobis[diphenyl(4-vinylphenyl)phosphane-κP]rhodium(I)

Hezron Ogutu ^a, Leo Kirsten ^a, Reinout Meijboom ^a,^*

PMCID: PMC3344302 PMID: 22590068

Abstract

In the title compound, trans-[RhCl(C₂₀H₁₇P)₂(CO)], the Rh^I atom is situated on a center of symmetry, resulting in a statistical 1:1 disorder of the chloride [Rh—Cl = 2.383 (2) Å] and carbonyl [Rh—C = 1.752 (7) Å] ligands. The distorted trans square-planar environment is completed by two P atoms [Rh—P = 2.3251 (4) Å] from two diphenyl(4-vinylphenyl)phosphane ligands. The vinyl group is disordered over two sets of sites in a 0.668 (10):0.332 (10) ratio. The crystal packing exhibits weak C—H⋯Cl and C—H⋯O hydrogen bonds and π–π interactions between the phenyl rings of neighbouring molecules, with a centroid–centroid distance of 3.682 (2) Å.

Related literature

For a review of rhodium Vaska {trans-[RhCl(CO)(PR ₃)₂]} compounds, see: Roodt et al. (2003 ▶). For related compounds, see: Angoletta (1959 ▶); Vaska & Di Luzio (1961 ▶); Chen et al. (1991 ▶); Kuwabara & Bau (1994 ▶); Otto et al. (2000 ▶); Otto (2001 ▶); Meijboom et al. (2005 ▶).

Experimental

Crystal data

[RhCl(C₂₀H₁₇P)₂(CO)]
M _r = 742.98
Triclinic,
a = 9.9030 (4) Å
b = 9.9310 (4) Å
c = 10.4150 (4) Å
α = 85.727 (2)°
β = 68.475 (2)°
γ = 62.295 (2)°
V = 837.85 (6) Å³
Z = 1
Cu Kα radiation
μ = 6.01 mm⁻¹
T = 100 K
0.10 × 0.08 × 0.06 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T _min = 0.107, T _max = 0.402
11163 measured reflections
2941 independent reflections
2850 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.024
wR(F ²) = 0.057
S = 1.04
2941 reflections
232 parameters
6 restraints
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT-Plus (Bruker, 2007 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812013669/cv5270sup1.cif

e-68-0m545-sup1.cif^{(27.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812013669/cv5270Isup2.hkl

e-68-0m545-Isup2.hkl^{(138.3KB, 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
C9B—H9B1⋯O01ⁱ	0.93	2.54	3.205 (11)	129
C14—H14⋯Cl1ⁱⁱ	0.93	2.79	3.660 (3)	157

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

Acknowledgments

Financial assistance from the South African National Research Foundation (SA NRF), the Research Fund of the University of Johannesburg, TESP and SASOL is gratefully acknowledged. Mr S. Enus is acknowledged for the synthesis of this compound.

supplementary crystallographic information

Comment

The original Vaska complex, trans-[IrCl(CO)(PPh₃)₂], was first reported in 1959 (Angoletta, 1959), but later correctly formulated by Vaska in 1961 (Vaska & Di Luzio, 1961) . This class of symmetrical square-planar complexes often crystallizes with the metal atom on a crystallographic inversion centre of symmetry, thus imposing a disordered packing arrangement (Otto, 2001;Otto et al., 2000; Chen et al.,1991; Kuwabara & Bau, 1994).These Vaska type complexes are useful model complexes and provide several probing methods, e.g. NMR and IR, to investigate the steric and electronic effects of novel group 15 ligands (Roodt et al., 2003).

Here we report the title compound, the i>trans-[RhClL₂(CO)](L = diphenyl(4-vinylphenyl)phosphane) complex crystallizes in the triclinic space group, P-1.The crystal structure of the title compound (Fig.1) shows the expected square planar geometry with the phosphane ligands trans to each other. The Rh^I atom is situated on a center of symmetry, resulting in a statistical 1:1 disorder of the chlorido [Rh—Cl 2.383 (2) Å] and carbonyl [Rh—C 1.752 (7) Å] ligands. The distorted trans square-planar environment is completed by two P atoms [Rh—P 2.3251 (4) Å] from two L ligands. The vinyl group is disordered over two sets of sites in a 0.668 (10):0.332 (10) ratio. The J coupling of (Rh-P) is 128 Hz which is in agreement with the coupling constants for other rhodium Vaska type complexes of this nature (Meijboom et al., 2005). The C01–Rh1–P2 angle of 92.99 (17) ° and the P2–Rh1–Cl1 of 94.46 (3) ° exemplifies the deviation from the ideal 90 ° square planar geometry.

The crystal packing exhibits weak intermolecular C—H···Cl and C—H···O hydrogen bonds (Table 1). There is a π–π interaction between the neighbouring phenyl ring centroids of C16-C21 and C16-C21 (2-x,1-y,1-z), respectively with the centroid-centroid distance of 3.682 (2) Å.

Experimental

Diphenylphosphinostyrene (0.15 g, 0.51 mmol) was dissolved in acetone (6 cm³). A solution of dichlorotetracarbonyldirhodium(I) (0.04 g, 0.13 mmol) in acetone was added to the phosphine solution. The mixture was stirred for 5 minutes, slow evaporation of the solvent afforded the title compound as a yellow crystalline solid. Spectroscopic analysis:³¹P{H} NMR (CDCl₃, 161.99 MHz, p.p.m.): 46.42 [d, ¹J(Rh—P) = 179.81 Hz]; IR ν(CO): 1957.96 cm^-1; (CD₂Cl₂) ν(CO): 1977.04 cm^-1.