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Acta Cryst. (2009). E65, m1341    [ doi:10.1107/S1600536809040744 ]

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

C. van Blerk and C. W. Holzapfel

Abstract top

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.

Comment top

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.

Related literature top

For related structures of similar palladium complexes and literature about their use in methoxycarbonylation reactions, see: Robertson et al. (2002); Van Leeuwen et al. (2003); Williams et al. (2008).

Experimental top

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 top

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.

Computing details top

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

Figures top
[Figure 1] 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).
trans-Bis[bis(2-methoxyphenyl)phenylphosphine- κP]dichloridopalladium(II) top
Crystal data top
[PdCl2(C20H19O2P)2]F(000) = 840
Mr = 821.94Dx = 1.424 Mg m−3
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 mm−1
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 top
Bruker SMART CCD
diffractometer		4750 independent reflections
Radiation source: fine-focus sealed tube3339 reflections with I > 2σ(I)
graphiteRint = 0.064
φ 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 top
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 = 1.02 w = 1/[σ2(Fo2) + (0.0441P)2]
where P = (Fo2 + 2Fc2)/3
4750 reflections(Δ/σ)max = 0.001
225 parametersΔρmax = 0.63 e Å−3
0 restraintsΔρmin = −0.37 e Å−3
0 constraints
Crystal data top
[PdCl2(C20H19O2P)2]V = 1917.24 (8) Å3
Mr = 821.94Z = 2
Monoclinic, P21/nMo Kα radiation
a = 9.1617 (2) ŵ = 0.75 mm−1
b = 12.7203 (3) ÅT = 296 K
c = 16.4939 (4) Å0.22 × 0.18 × 0.12 mm
β = 94.114 (1)°
Data collection top
Bruker SMART CCD
diffractometer		4750 independent reflections
Absorption correction: multi-scan
(APEX AXScale; Bruker, 2008)		3339 reflections with I > 2σ(I)
Tmin = 0.853, Tmax = 0.916Rint = 0.064
23435 measured reflectionsθmax = 28.3°
Refinement top
R[F2 > 2σ(F2)] = 0.036H-atom parameters constrained
wR(F2) = 0.089Δρmax = 0.63 e Å−3
S = 1.02Δρmin = −0.37 e Å−3
4750 reflectionsAbsolute structure: ?
225 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
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) top
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, °) top
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.
Table 1
Selected geometric parameters (Å, °) top
P1—Pd12.3458 (6)Cl1—Pd12.3048 (7)
Cl1—Pd1—P193.24 (2)Cl1i—Pd1—P186.76 (2)
Symmetry codes: (i) −x, −y, −z.
Acknowledgements top

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

references
References top

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