trans-Dichloridobis(triphenyl­phosphine)palladium(II)

Josefina Pons; Jordi García-Antón; Xavier Solans; Mercè Font-Bardia; Josep Ros

doi:10.1107/S1600536808008337

. 2008 Apr 4;64(Pt 5):m621. doi: 10.1107/S1600536808008337

trans-Dichloridobis(triphenylphosphine)palladium(II)¹

Josefina Pons ^a,^*, Jordi García-Antón ^a, Xavier Solans ^b, Mercè Font-Bardia ^b, Josep Ros ^a

PMCID: PMC2961313 PMID: 21202176

Abstract

The title compound, [PdCl₂{P(C₆H₅)₃}₂], has a slightly distorted square-planar geometry, with the chloride ligands coordinated in a trans configuration. The Pd atom is located on a centre of inversion.

Related literature

For related literature, see: Ferguson et al. (1982 ▶); Kitano et al. (1983 ▶); La Monica & Ardizzoia (1997 ▶); Montoya et al. (2005 ▶); Montoya et al. (2006 ▶); Mukherjee (2000 ▶); Oilunkaniemi et al. (2003 ▶); Stark et al. (1997 ▶); Steyl (2006 ▶); Trofimenko (1972 ▶, 1986 ▶).

Experimental

Crystal data

[PdCl₂(C₁₈H₁₅P)₂]
M _r = 701.84
Monoclinic,
a = 9.296 (5) Å
b = 19.889 (8) Å
c = 10.621 (6) Å
β = 121.71 (4)°
V = 1670.6 (15) Å³
Z = 2
Mo Kα radiation
μ = 0.83 mm⁻¹
T = 293 (2) K
0.2 × 0.17 × 0.16 mm

Data collection

Mar Research MAR345 diffractometer with image-plate detector
Absorption correction: multi-scan (SADABS; Bruker, 1999 ▶) T _min = 0.85, T _max = 0.87
4898 measured reflections
4898 independent reflections
3143 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.077
S = 0.93
4898 reflections
187 parameters
7 restraints
H-atom parameters constrained
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Data collection: MARXDS (Kabsch, 1988 ▶); cell refinement: AUTOMAR (Kabsch, 1988 ▶); data reduction: MARSCALE (Kabsch, 1988 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808008337/bt2685sup1.cif

e-64-0m621-sup1.cif^{(17KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808008337/bt2685Isup2.hkl

e-64-0m621-Isup2.hkl^{(235.1KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Pd—Cl	2.3111 (13)
Pd—P	2.3721 (10)

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Cl—Pd—P	87.62 (4)
Clⁱ—Pd—P	92.38 (4)

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Cl—Pd—P—C1	41.9 (2)
Cl—Pd—P—C13	−75.7 (2)
Cl—Pd—P—C7	163.9 (2)

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Symmetry code: (i) Inline graphic .

Acknowledgments

Support by the Spanish Ministerio de Educación y Cultura (Project CTQ2007–639137) is gratefully aknowledged.

supplementary crystallographic information

Comment

The coordination chemistry of pyrazole derived ligands has been extensively studied in recent years (Trofimenko, 1972, 1986; La Monica et al., 1997; Mukherjee, 2000). Recently, in our laboratory the synthesis and characterization of a family of 1,3,5-pyrazole derived ligands have been developed (Montoya et al. 2005) and we have studied the reactivity towards divalent metal ions. The reaction of [PdCl₂L¹] (L¹ = 2-(1-ethyl-5-phenyl-1H-pyrazol-3-yl)pyridine with AgBF₄ followed by the addition of PPh₃ and NaBPh₄ yields the compound [Pd(L¹)(PPh₃)₂](BPh₄)₂ (Montoya et al., 2006). The title compound was obtained when the triphenylphosphine ligand was added before the precipitation of the chloride ions with AgBF₄. In this way, PPh₃ ligands displace L¹ to form trans-[PdCl₂(PPh₃)₂] (1).

Related compounds are trans-[PdCl₂(PPh₃)₂] (2) (Ferguson et al., 1982), trans-[PdCl₂(PPh₃)₂].C₆H₄Cl₂ (Kitano et al.,1983), trans-[PdCl₂(PPh₃)₂].2CHCl₃ (Stark et al., 1997), trans-[PdCl₂(PPh₃)₂].CH₂Cl₂ (Oilunkaniemi et al., 2003), and trans-[PdCl₂(PPh₃)₂].C₂H₄Cl₂ (Steyl, 2006). There are no solvent molecules present in the structure described in this paper. The same behaviour was found for the structure described by Ferguson (2), but differences have been found in the crystal systems and space groups [triclinic P1 (2); monoclinic P2₁/c, (1)]. Moreover, the Pd—Cl and Pd—P bond distances (2.3111 (13) Å and 2.3721 (10) Å, respectively) in complex (1) are slightly longer than those found in complex (2) (2.290 (1) Å and 2.337 (1) Å, respectively).

Experimental

Treatment of 0.14 mmol (0.060 g) of [PdCl₂(L¹)] (L¹ = 2-(1-ethyl-5-phenyl-1H-pyrazol-3-yl)pyridine) with 0.28 mmol (0.054 g) of PPh₃ in 10 ml of dichloromethane and 10 ml of methanol provokes the displacement of the pyrazolic ligand from the coordinative sphere of the metallic cation and the formation of trans-[PdCl₂(PPh₃)₂]. This complex precipitates as a yellow solid and was filtered and dried under vacuum. Single crystals were obtained by recrystallization of the complex in dichloromethane/diethyl ether 1:1. Yield: 0.080 g (81%) - C₃₆H₃₀Cl₂P₂Pd (701.84). % C, 61.60; H, 4.30; found: C, 61.33; H, 4.42;. IR (KBr, cm^-1): ν (C—H)_ar 3047; δ (C—H)_ar 1437; δ (C—H)_oop 693. IR (polyethylene, cm^-1): ν 376, 358 (Pd—P), ν (Pd—Cl). ¹H NMR (250 MHz, [D₁]-chloroform solution) δ = 7.71 (m, 2H, PPh₃ortho), 7.44–7.35 (m, 3H, PPh₃). ¹³C{¹H} NMR (63 MHz, [D₁]-chloroform solution) δ = 135.5, 131.0, 130.0, 128.5 (PPh₃). ³¹P{¹H} NMR (81 MHz, [D₁]-chloroform solution) δ = -21.1 (s, PPh₃).