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Acta Crystallogr Sect E Struct Rep Online. 2009 November 1; 65(Pt 11): m1341.
Published online 2009 October 10. doi:  10.1107/S1600536809040744
PMCID: PMC2971441

trans-Bis[bis­(2-methoxy­phen­yl)phenyl­phosphine-κP]dichloridopalladium(II)

Abstract

The structure of the title compound, [PdCl2(C20H19O2P)2], shows a square-planar geometry for the PdII ion within a Cl2Pd[PPh(PhOMe)2]2 ligand set. The PdII atom sits on an inversion centre and therefore the asymmetric unit contains the PdII atom, one Cl atom and one bis­(2-methoxy­phen­yl)phenyl­phosphine ligand. The trans arrangement of ligands is also imposed by symmetry.

Related literature

For related structures of similar palladium complexes and their use in methoxy­carbonyl­ation reactions, see: Robertson & Cole-Hamilton (2002 [triangle]); Van Leeuwen et al. (2003 [triangle]); Williams et al. (2008 [triangle]).

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Object name is e-65-m1341-scheme1.jpg

Experimental

Crystal data

  • [PdCl2(C20H19O2P)2]
  • M r = 821.94
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-m1341-efi1.jpg
  • a = 9.1617 (2) Å
  • b = 12.7203 (3) Å
  • c = 16.4939 (4) Å
  • β = 94.114 (1)°
  • V = 1917.24 (8) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.75 mm−1
  • T = 296 K
  • 0.22 × 0.18 × 0.12 mm

Data collection

  • Bruker SMART CCD diffractometer
  • Absorption correction: multi-scan (APEX AXScale; Bruker, 2008 [triangle]) T min = 0.853, T max = 0.916
  • 23435 measured reflections
  • 4750 independent reflections
  • 3339 reflections with I > 2σ(I)
  • R int = 0.064

Refinement

  • R[F 2 > 2σ(F 2)] = 0.036
  • wR(F 2) = 0.089
  • S = 1.02
  • 4750 reflections
  • 225 parameters
  • H-atom parameters constrained
  • Δρmax = 0.63 e Å−3
  • Δρmin = −0.38 e Å−3

Data collection: SMART-NT (Bruker, 1999 [triangle]); cell refinement: SAINT (Bruker, 2008 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]) and Mercury (Macrae et al., 2006 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2009 [triangle]).

Table 1
Selected geometric parameters (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809040744/bh2252sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809040744/bh2252Isup2.hkl

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

Acknowledgments

The authors acknowledge the University of the Witwaters­rand for their facilities and the use of the diffractometer in the Jan Boeyens Structural Chemistry Laboratory.

supplementary crystallographic information

Comment

The palladium-catalysed methoxycarbonylation (Robertson & Cole-Hamilton, 2002) of 1-alkenes is an active area of research. The preferred (pre)-catalysts of general structure (Ar3P)2PdX2 (X = Cl, DMS, OTf, etc.) are either preformed or generated in situ. The X-ray structures (Van Leeuwen et al., 2003; Williams et al., 2008) of several of this class of palladium(II) complexes have been determined. Only some of these have found application in the catalysis of the methoxycarbonylation reaction, but their use results mainly in the formation of linear esters (Robertson & Cole-Hamilton, 2002). However, we have identified some palladium(II) complexes which catalyse the regioselective formation of branched esters. We report here the structure of one of these.

The structure of the title compound, [PdCl2(C40H38P2O4)], shows a square planar geometry for the PdII ion within the Cl2(PPh(PhOMe)2) ligand set. The palladium atom sits on a centre of inversion and therefore the asymmetric unit contains the palladium atom, one chlorine atom and one bis-(2-methoxyphenyl)phenylphosphine ligand. Figure 1 shows the molecular structure of the title compound.

Experimental

Bis-(2-methoxyphenyl)phenylphosphine (1.288 g, 4 mmol) was added to a solution of palladium(II) chloride (354 mg, 2 mmol) and anhydrous lithium chloride (168 mg, 4 mmol) in methanol (15 ml). The mixture was refluxed in an atmosphere of nitrogen until all the phosphine reagent had reacted and a light yellow product had formed (ca. 45 min). The reaction mixture was cooled and the product collected by filtration, washed with fresh methanol and dried under vacuum. The crude product (1.37 g) was dissolved in dichloromethane and crystallization of the title compound was carried out by diethyl ether vapour diffusion into the dichloromethane. The crystals of the title compound were pale yellow blocks (m.p. > 503 K, decomp.) and a suitable crystal was selected for the single-crystal X-ray diffraction analysis.

Refinement

H atoms were geometrically positioned and refined in the riding-model approximation, with C—H = 0.93–0.97 Å, and Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C). The highest peak in the final difference map is 2.20 Å from H37A and the deepest hole is 0.31 Å from Pd1.

Figures

Fig. 1.
Molecular structure of (I) with displacement ellipsoids drawn at the 50% probability level. Atoms labelled with (i) are at symmetry position (-x, -y, -z).

Crystal data

[PdCl2(C20H19O2P)2]F(000) = 840
Mr = 821.94Dx = 1.424 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 5078 reflections
a = 9.1617 (2) Åθ = 2.5–24.7°
b = 12.7203 (3) ŵ = 0.75 mm1
c = 16.4939 (4) ÅT = 296 K
β = 94.114 (1)°Block, yellow
V = 1917.24 (8) Å30.22 × 0.18 × 0.12 mm
Z = 2

Data collection

Bruker SMART CCD diffractometer4750 independent reflections
Radiation source: fine-focus sealed tube3339 reflections with I > 2σ(I)
graphiteRint = 0.064
[var phi] and ω scansθmax = 28.3°, θmin = 2.0°
Absorption correction: multi-scan (APEX AXScale; Bruker, 2008)h = −12→12
Tmin = 0.853, Tmax = 0.916k = −16→16
23435 measured reflectionsl = −21→21

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.089H-atom parameters constrained
S = 1.02w = 1/[σ2(Fo2) + (0.0441P)2] where P = (Fo2 + 2Fc2)/3
4750 reflections(Δ/σ)max = 0.001
225 parametersΔρmax = 0.63 e Å3
0 restraintsΔρmin = −0.37 e Å3
0 constraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
C110.0228 (3)0.1927 (2)−0.15944 (16)0.0323 (6)
C120.0094 (3)0.1268 (2)−0.22659 (16)0.0401 (7)
H12−0.04320.0646−0.22400.048*
C130.0734 (3)0.1526 (3)−0.29741 (18)0.0505 (8)
H130.06470.1072−0.34170.061*
C140.1500 (3)0.2454 (3)−0.3024 (2)0.0528 (8)
H140.19270.2628−0.35010.063*
C150.1626 (3)0.3112 (3)−0.2373 (2)0.0505 (8)
H150.21280.3744−0.24090.061*
C160.1016 (3)0.2850 (2)−0.16577 (18)0.0426 (7)
H160.11360.3299−0.12130.051*
C21−0.2607 (3)0.1459 (2)−0.10562 (17)0.0363 (6)
C22−0.3400 (3)0.0578 (2)−0.08536 (18)0.0434 (7)
H22−0.29540.0076−0.05080.052*
C23−0.4839 (3)0.0426 (3)−0.1152 (2)0.0569 (9)
H23−0.5358−0.0163−0.10020.068*
C24−0.5481 (4)0.1156 (3)−0.1671 (2)0.0670 (10)
H24−0.64440.1055−0.18760.080*
C25−0.4735 (4)0.2040 (3)−0.1898 (2)0.0631 (10)
H25−0.51910.2525−0.22540.076*
C26−0.3300 (3)0.2201 (3)−0.15904 (19)0.0472 (8)
C27−0.3017 (6)0.3742 (4)−0.2385 (3)0.1117 (19)
H27A−0.31800.3354−0.28820.167*
H27B−0.23110.4286−0.24540.167*
H27C−0.39210.4052−0.22450.167*
C31−0.0464 (3)0.2692 (2)−0.00191 (17)0.0403 (7)
C32−0.1582 (4)0.3370 (2)0.0142 (2)0.0518 (8)
H32−0.25100.3276−0.01140.062*
C33−0.1318 (5)0.4201 (3)0.0691 (2)0.0707 (11)
H33−0.20660.46640.07960.085*
C340.0048 (6)0.4326 (3)0.1071 (2)0.0805 (13)
H340.02120.48690.14440.097*
C350.1175 (5)0.3675 (3)0.0916 (2)0.0737 (12)
H350.20990.37790.11750.088*
C360.0933 (4)0.2854 (2)0.03693 (19)0.0505 (8)
C370.3458 (4)0.2356 (4)0.0401 (3)0.1033 (17)
H37A0.37050.30480.02240.155*
H37B0.40600.18470.01540.155*
H37C0.36180.23120.09810.155*
O1−0.2494 (2)0.30626 (18)−0.17624 (15)0.0639 (7)
O20.1969 (2)0.21487 (18)0.01702 (15)0.0628 (7)
P1−0.06893 (7)0.15556 (5)−0.06890 (4)0.03007 (16)
Cl10.12498 (8)−0.06305 (6)−0.10623 (4)0.04534 (19)
Pd10.00000.00000.00000.02642 (9)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C110.0277 (13)0.0311 (14)0.0378 (14)0.0047 (11)0.0009 (11)0.0057 (11)
C120.0412 (16)0.0401 (16)0.0384 (16)−0.0050 (13)−0.0002 (13)0.0031 (13)
C130.056 (2)0.059 (2)0.0359 (16)0.0035 (16)0.0020 (15)0.0028 (15)
C140.0448 (19)0.069 (2)0.0461 (18)0.0056 (17)0.0128 (15)0.0177 (17)
C150.0432 (18)0.0463 (19)0.063 (2)−0.0063 (15)0.0130 (16)0.0168 (16)
C160.0434 (17)0.0356 (16)0.0492 (17)−0.0033 (13)0.0056 (14)0.0043 (13)
C210.0268 (14)0.0406 (16)0.0415 (15)0.0064 (12)0.0030 (12)0.0073 (12)
C220.0336 (16)0.0468 (18)0.0492 (17)0.0012 (13)0.0001 (13)0.0083 (14)
C230.0321 (17)0.062 (2)0.076 (2)−0.0062 (15)−0.0007 (16)0.0080 (19)
C240.0341 (18)0.091 (3)0.074 (2)0.0017 (19)−0.0093 (17)0.004 (2)
C250.0407 (19)0.080 (3)0.067 (2)0.0151 (18)−0.0095 (17)0.022 (2)
C260.0381 (17)0.0505 (19)0.0529 (18)0.0081 (14)0.0027 (14)0.0131 (15)
C270.128 (4)0.086 (3)0.114 (4)−0.004 (3)−0.035 (3)0.063 (3)
C310.0531 (18)0.0263 (14)0.0425 (16)0.0021 (12)0.0100 (15)0.0037 (12)
C320.062 (2)0.0367 (17)0.060 (2)0.0031 (15)0.0236 (17)0.0025 (15)
C330.099 (3)0.039 (2)0.079 (3)0.009 (2)0.046 (2)−0.0043 (19)
C340.124 (4)0.054 (3)0.064 (3)−0.007 (3)0.016 (3)−0.018 (2)
C350.102 (3)0.049 (2)0.068 (2)−0.010 (2)−0.014 (2)−0.0157 (19)
C360.067 (2)0.0352 (16)0.0484 (18)−0.0089 (15)−0.0040 (16)−0.0039 (14)
C370.059 (3)0.094 (3)0.151 (4)−0.009 (2)−0.033 (3)−0.026 (3)
O10.0490 (13)0.0574 (14)0.0837 (17)0.0081 (11)−0.0064 (12)0.0361 (13)
O20.0521 (14)0.0522 (14)0.0802 (16)0.0009 (11)−0.0218 (12)−0.0140 (12)
P10.0294 (3)0.0265 (3)0.0342 (4)0.0024 (3)0.0015 (3)0.0036 (3)
Cl10.0549 (5)0.0435 (4)0.0395 (4)0.0124 (3)0.0169 (3)0.0021 (3)
Pd10.02524 (14)0.02514 (14)0.02887 (14)0.00229 (12)0.00193 (10)0.00150 (12)

Geometric parameters (Å, °)

C11—C161.386 (4)C27—O11.400 (4)
C11—C121.387 (4)C27—H27A0.9600
C11—P11.827 (3)C27—H27B0.9600
C12—C131.383 (4)C27—H27C0.9600
C12—H120.9300C31—C321.379 (4)
C13—C141.379 (4)C31—C361.405 (4)
C13—H130.9300C31—P11.822 (3)
C14—C151.361 (5)C32—C331.402 (5)
C14—H140.9300C32—H320.9300
C15—C161.382 (4)C33—C341.368 (6)
C15—H150.9300C33—H330.9300
C16—H160.9300C34—C351.362 (6)
C21—C221.390 (4)C34—H340.9300
C21—C261.410 (4)C35—C361.388 (4)
C21—P11.821 (3)C35—H350.9300
C22—C231.387 (4)C36—O21.363 (4)
C22—H220.9300C37—O21.414 (4)
C23—C241.367 (5)C37—H37A0.9600
C23—H230.9300C37—H37B0.9600
C24—C251.381 (5)C37—H37C0.9600
C24—H240.9300P1—Pd12.3458 (6)
C25—C261.390 (4)Cl1—Pd12.3048 (7)
C25—H250.9300Pd1—Cl1i2.3048 (7)
C26—O11.363 (4)Pd1—P1i2.3458 (6)
C16—C11—C12117.9 (3)H27A—C27—H27C109.5
C16—C11—P1123.6 (2)H27B—C27—H27C109.5
C12—C11—P1118.5 (2)C32—C31—C36119.0 (3)
C13—C12—C11120.9 (3)C32—C31—P1124.0 (3)
C13—C12—H12119.6C36—C31—P1116.9 (2)
C11—C12—H12119.6C31—C32—C33120.0 (3)
C14—C13—C12120.1 (3)C31—C32—H32120.0
C14—C13—H13119.9C33—C32—H32120.0
C12—C13—H13119.9C34—C33—C32119.6 (4)
C15—C14—C13119.6 (3)C34—C33—H33120.2
C15—C14—H14120.2C32—C33—H33120.2
C13—C14—H14120.2C35—C34—C33121.6 (4)
C14—C15—C16120.6 (3)C35—C34—H34119.2
C14—C15—H15119.7C33—C34—H34119.2
C16—C15—H15119.7C34—C35—C36119.5 (4)
C15—C16—C11120.9 (3)C34—C35—H35120.3
C15—C16—H16119.5C36—C35—H35120.3
C11—C16—H16119.5O2—C36—C35124.8 (3)
C22—C21—C26118.1 (3)O2—C36—C31114.9 (3)
C22—C21—P1118.9 (2)C35—C36—C31120.3 (3)
C26—C21—P1122.9 (2)O2—C37—H37A109.5
C23—C22—C21121.8 (3)O2—C37—H37B109.5
C23—C22—H22119.1H37A—C37—H37B109.5
C21—C22—H22119.1O2—C37—H37C109.5
C24—C23—C22118.9 (3)H37A—C37—H37C109.5
C24—C23—H23120.6H37B—C37—H37C109.5
C22—C23—H23120.6C26—O1—C27119.1 (3)
C23—C24—C25121.6 (3)C36—O2—C37119.2 (3)
C23—C24—H24119.2C21—P1—C31108.64 (14)
C25—C24—H24119.2C21—P1—C11103.58 (12)
C24—C25—C26119.7 (3)C31—P1—C11104.58 (13)
C24—C25—H25120.2C21—P1—Pd1108.91 (9)
C26—C25—H25120.2C31—P1—Pd1111.13 (9)
O1—C26—C25123.7 (3)C11—P1—Pd1119.37 (8)
O1—C26—C21116.2 (3)Cl1—Pd1—Cl1i180.00 (4)
C25—C26—C21120.0 (3)Cl1—Pd1—P1i86.76 (2)
O1—C27—H27A109.5Cl1i—Pd1—P1i93.24 (2)
O1—C27—H27B109.5Cl1—Pd1—P193.24 (2)
H27A—C27—H27B109.5Cl1i—Pd1—P186.76 (2)
O1—C27—H27C109.5P1i—Pd1—P1180.00 (5)
C16—C11—C12—C130.2 (4)P1—C31—C36—C35−177.1 (3)
P1—C11—C12—C13178.3 (2)C25—C26—O1—C27−11.5 (5)
C11—C12—C13—C14−0.9 (4)C21—C26—O1—C27169.7 (3)
C12—C13—C14—C150.2 (5)C35—C36—O2—C37−12.9 (5)
C13—C14—C15—C161.2 (5)C31—C36—O2—C37167.9 (3)
C14—C15—C16—C11−1.9 (5)C22—C21—P1—C31−117.1 (2)
C12—C11—C16—C151.1 (4)C26—C21—P1—C3167.9 (3)
P1—C11—C16—C15−176.8 (2)C22—C21—P1—C11132.1 (2)
C26—C21—C22—C23−1.0 (5)C26—C21—P1—C11−42.9 (3)
P1—C21—C22—C23−176.2 (3)C22—C21—P1—Pd14.1 (3)
C21—C22—C23—C241.2 (5)C26—C21—P1—Pd1−170.9 (2)
C22—C23—C24—C25−0.5 (6)C32—C31—P1—C21−2.3 (3)
C23—C24—C25—C26−0.4 (6)C36—C31—P1—C21175.8 (2)
C24—C25—C26—O1−178.1 (3)C32—C31—P1—C11107.8 (3)
C24—C25—C26—C210.6 (5)C36—C31—P1—C11−74.1 (2)
C22—C21—C26—O1178.9 (3)C32—C31—P1—Pd1−122.1 (2)
P1—C21—C26—O1−6.1 (4)C36—C31—P1—Pd156.0 (2)
C22—C21—C26—C250.0 (5)C16—C11—P1—C21119.4 (2)
P1—C21—C26—C25175.0 (3)C12—C11—P1—C21−58.5 (2)
C36—C31—C32—C33−0.5 (5)C16—C11—P1—C315.7 (3)
P1—C31—C32—C33177.5 (2)C12—C11—P1—C31−172.3 (2)
C31—C32—C33—C34−0.7 (5)C16—C11—P1—Pd1−119.4 (2)
C32—C33—C34—C351.4 (6)C12—C11—P1—Pd162.7 (2)
C33—C34—C35—C36−0.9 (6)C21—P1—Pd1—Cl1103.82 (10)
C34—C35—C36—O2−179.6 (3)C31—P1—Pd1—Cl1−136.53 (11)
C34—C35—C36—C31−0.3 (6)C11—P1—Pd1—Cl1−14.71 (10)
C32—C31—C36—O2−179.7 (3)C21—P1—Pd1—Cl1i−76.18 (10)
P1—C31—C36—O22.2 (4)C31—P1—Pd1—Cl1i43.47 (11)
C32—C31—C36—C351.0 (5)C11—P1—Pd1—Cl1i165.29 (10)

Symmetry codes: (i) −x, −y, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BH2252).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bruker (1999). SMART-NT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2008). APEX AXScale and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst.39, 453–457.
  • Robertson, R. A. M. & Cole-Hamilton, D. J. (2002). Coord. Chem Rev 225, 67–90.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Van Leeuwen, P. W. N. M., Zuideveld, M. A., Swennenhuis, B. H., Freixa, Z., Kamer, P. C. J., Goubitz, K., Fraanje, J., Lutz, M. & Spek, A. L. (2003). J. Am. Chem. Soc 125, 5523–5539. [PubMed]
  • Westrip, S. P. (2009). publCIF. In preparation.
  • Williams, D. B. G., Shaw, M. L., Green, M. J. & Holzapfel, C. W. (2008). Angew. Chem. Int. Ed 47, 560–563. [PubMed]

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