trans-Di­chloridobis(triiso­propyl­phosphine-κP)palladium(II)

The title compound, [PdCl₂(C₉H₂₁P)₂], is a centrosymmetric mononuclear palladium(II) complex. The Pd^II atom, which lies on an inversion center, is in a square-planar geometry.

Related literature

For trans-dichlorido-bis­(triphenyl­phosphine)palladium(II), see: Ferguson et al. (1982). For trans-dichlorido-bis­[diphenyl (cyclo­hexyl)phosphine]palladium(II), see: Meij et al. (2003). For trans-dichlorido-bis­[diphen­yl(p-tol­yl)phosphine]palla­dium(II), see: Steyl et al. (2006). For related literature, see: Baum et al. (2006); Bedford et al. (2003); Schultz et al. (1992).

Experimental

Crystal data

• [PdCl₂(C₉H₂₁P)₂]

• M_r = 497.76

• Monoclinic, P 2₁ /c

• a = 8.0919 (3) Å

• b = 8.9176 (4) Å

• c = 16.1920 (6) Å

• β = 92.552 (3)°

• V = 1167.26 (8) ų

• Z = 2

• Mo Kα radiation

• μ = 1.16 mm⁻¹

• T = 120 (2) K

• 0.15 × 0.09 × 0.02 mm

Data collection

• Oxford Diffraction KM-4-CCD diffractometer

• Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2006) T_min = 0.791, T_max = 0.955

• 7043 measured reflections

• 2175 independent reflections

• 1985 reflections with I > 2σ(I)

• R_int = 0.042

Refinement

• R[F² > 2σ(F²)] = 0.030

• wR(F²) = 0.089

• S = 1.13

• 2175 reflections

• 112 parameters

• H-atom parameters constrained

• Δρ_max = 1.44 e Å⁻³

• Δρ_min = −0.65 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Supporting information

S1. Comment

Expanding our work upon the reactivity of [(R₃P)₂MCl₂] (M = Ni, Pd, Pt) towards ^tBu₂P–PLi–P^tBu₂ (Baum et al., 2006), we have studied the reaction of ^tBu₂P-PLi-P(^tBu)(SiMe₃).2THF with [trans-(ⁱPr₃P)₂PdCl₂] in a 1:1 molar ratio in THF. Unreacted [trans-(ⁱPr₃P)₂PdCl₂] was isolated from the toluene solution of reaction product as yellow crystals.

The molecular structure of the title compound is shown in Fig.1. The mononuclear complex is centrosymmetric, with the Pd^II atom lying on an inversion centre. The geometry around the Pd^II atom is strictly square-planar. The Pd—P [2.3603 (6) Å] and Pd—Cl [2.3030 (6) Å] distances and P—Pd—Cl [89.92 (2)° and 90.18 (2)°] angles are typical for [trans-(R₃P)₂PdCl₂] (Ferguson et al., 1982; Meij et al., 2003; Steyl et al., 2006; Bedford et al., 2003). The distances in [cis-(R₃P)₂PdCl₂] differ significantly from those reported for [trans-(R₃P)₂PdCl₂]. For [cis-(Me₃P)₂PdCl₂], the related distances are 2.374 (3) Å (Pd—Cl, mean value) and 2.258 (2) Å (Pd—P, mean value) (Schultz et al., 1992). The elongation of Pd—Cl distances in cis isomers compared to trans isomers is due to a strong trans effect of PR₃ ligand in a position trans to Cl ligand. The shortening of Pd—P distances in cis isomers are caused by a lack of a second phosphine ligand in the trans position. The Cl ligand exerts only weak trans effect.

Related literature

For trans-dichloro-bis(triphenylphosphine)palladium(II), see: Ferguson et al. (1982). For trans-dichloro-bis[diphenyl (cyclohexyl)phosphine]palladium(II), see: Meij et al. (2003). For trans-dichloro-bis[diphenyl(p-tolyl)phosphine] palladium(II), see: Steyl et al. (2006). For related literature, see: Baum et al. (2006); Bedford et al. (2003); Schultz et al. (1992).

S2. Experimental

A solution of ^tBu₂P-PLi-P(^tBu)(SiMe₃).2THF (139 mg, 0.285 mmol) in tetrahydrofuran (THF, 2 mL) was added dropwise to a suspension of yellow powder of [(ⁱPr₃P)₂PdCl₂] (139 mg, 0.28 mmol) in THF (2 ml) at room temperature. The mixture turned red. After allowed to stand at room temperature for 1 d, the mixture was dried under vacuum at 1 mTorr for 1 h, and the residue was dissolved in toluene (4 ml) and filtered. The solution was kept at 277 K for 2d to obtain small yellow crystals of [trans-(ⁱPr₃P)₂PdCl₂].

S3. Refinement

All H atoms were positioned geometrically and refined using a riding model, with C–H = 0.98 Å and U_iso(H) = 1.2U_eq(C) or 1.5U_eq(methyl C). The highest residual electron-density peak is located 0.86 Å from atom Cl1.

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. A view of the title molecule, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity. Unlabelled atoms are related to labelled atoms by the symmetry operation (1-x, 1-y, -z).
	Fig. 2. Crystal packing of the title compound, viewed approximately along the b axis.

trans-Dichloridobis(triisopropylphosphine-κP)palladium(II)

Crystal data

[PdCl2(C9H21P)2]	F(000) = 520
Mr = 497.76	Dx = 1.416 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7947 reflections
a = 8.0919 (3) Å	θ = 2.3–32.5°
b = 8.9176 (4) Å	µ = 1.16 mm^−1
c = 16.1920 (6) Å	T = 120 K
β = 92.552 (3)°	Prism, colourless
V = 1167.26 (8) Å^3	0.15 × 0.09 × 0.02 mm
Z = 2

Data collection

Oxford Diffraction KM-4-CCD diffractometer	2175 independent reflections
Graphite monochromator	1985 reflections with I > 2σ(I)
Detector resolution: 8.1883 pixels mm^-1	Rint = 0.042
0.75° wide ω scans	θmax = 25.5°, θmin = 2.5°
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2006)	h = −9→9
Tmin = 0.791, Tmax = 0.955	k = −10→6
7043 measured reflections	l = −19→19

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.089	H-atom parameters constrained
S = 1.13	w = 1/[σ^2(Fo^2) + (0.0568P)^2 + 0.2267P] where P = (Fo^2 + 2Fc^2)/3
2175 reflections	(Δ/σ)max = 0.001
112 parameters	Δρmax = 1.44 e Å^−3
0 restraints	Δρmin = −0.65 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Pd1	0.5	0.5	0	0.01758 (14)
P1	0.62758 (8)	0.33350 (7)	0.09656 (4)	0.01777 (17)
Cl1	0.53892 (10)	0.69501 (7)	0.09206 (4)	0.0358 (2)
C1	0.4699 (3)	0.2487 (3)	0.16092 (14)	0.0218 (5)
H1	0.529	0.1858	0.204	0.026*
C2	0.3743 (3)	0.3692 (3)	0.20534 (17)	0.0322 (6)
H2A	0.3178	0.4347	0.1645	0.048*
H2B	0.4512	0.4288	0.2404	0.048*
H2C	0.2925	0.3217	0.2397	0.048*
C3	0.3525 (4)	0.1470 (3)	0.11119 (18)	0.0352 (7)
H3A	0.2641	0.1132	0.1462	0.053*
H3B	0.4134	0.0599	0.0916	0.053*
H3C	0.3043	0.2023	0.0637	0.053*
C4	0.7288 (3)	0.1727 (3)	0.04740 (15)	0.0222 (5)
H4	0.639	0.1221	0.0134	0.027*
C5	0.7990 (4)	0.0510 (3)	0.10597 (17)	0.0336 (6)
H5A	0.8222	−0.0396	0.0742	0.05*
H5B	0.7182	0.0277	0.1474	0.05*
H5C	0.9015	0.0871	0.1337	0.05*
C6	0.8569 (4)	0.2198 (3)	−0.01420 (17)	0.0355 (7)
H6A	0.9591	0.2505	0.0159	0.053*
H6B	0.8136	0.304	−0.0475	0.053*
H6C	0.8802	0.1352	−0.0505	0.053*
C7	0.7729 (3)	0.4281 (3)	0.17166 (15)	0.0248 (5)
H7	0.7088	0.512	0.1959	0.03*
C8	0.8372 (4)	0.3339 (3)	0.24483 (18)	0.0393 (7)
H8A	0.9122	0.2566	0.2254	0.059*
H8B	0.7439	0.2861	0.2711	0.059*
H8C	0.8968	0.3985	0.285	0.059*
C9	0.9156 (5)	0.5020 (3)	0.1284 (2)	0.0403 (9)
H9A	0.9727	0.5725	0.1663	0.06*
H9B	0.8723	0.5562	0.0794	0.06*
H9C	0.9936	0.4249	0.1116	0.06*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.0209 (2)	0.0166 (2)	0.01496 (18)	−0.00014 (9)	−0.00173 (12)	−0.00049 (8)
P1	0.0189 (3)	0.0187 (3)	0.0156 (3)	0.0011 (2)	−0.0004 (2)	0.0009 (2)
Cl1	0.0575 (5)	0.0223 (3)	0.0259 (3)	0.0064 (3)	−0.0155 (3)	−0.0074 (3)
C1	0.0226 (12)	0.0224 (11)	0.0205 (12)	0.0007 (10)	0.0030 (10)	0.0034 (10)
C2	0.0311 (14)	0.0334 (14)	0.0329 (14)	0.0026 (13)	0.0120 (12)	−0.0013 (12)
C3	0.0326 (15)	0.0392 (16)	0.0344 (15)	−0.0152 (13)	0.0068 (12)	−0.0051 (12)
C4	0.0226 (12)	0.0216 (12)	0.0225 (12)	0.0035 (10)	0.0023 (10)	−0.0014 (10)
C5	0.0391 (17)	0.0292 (14)	0.0329 (15)	0.0120 (14)	0.0053 (13)	0.0000 (13)
C6	0.0354 (16)	0.0381 (16)	0.0341 (15)	0.0051 (13)	0.0129 (13)	0.0002 (12)
C7	0.0252 (13)	0.0262 (13)	0.0225 (12)	−0.0011 (11)	−0.0049 (10)	−0.0019 (10)
C8	0.0494 (18)	0.0365 (15)	0.0301 (15)	0.0017 (14)	−0.0196 (13)	−0.0004 (12)
C9	0.0307 (19)	0.052 (2)	0.0378 (19)	−0.0199 (12)	−0.0029 (16)	−0.0036 (12)

Geometric parameters (Å, º)

Pd1—Cl1^i	2.3030 (6)	C4—C5	1.533 (4)
Pd1—Cl1	2.3030 (6)	C4—H4	1
Pd1—P1	2.3603 (6)	C5—H5A	0.98
Pd1—P1^i	2.3603 (6)	C5—H5B	0.98
P1—C1	1.845 (2)	C5—H5C	0.98
P1—C4	1.849 (2)	C6—H6A	0.98
P1—C7	1.856 (2)	C6—H6B	0.98
C1—C3	1.518 (4)	C6—H6C	0.98
C1—C2	1.523 (3)	C7—C8	1.525 (4)
C1—H1	1	C7—C9	1.528 (4)
C2—H2A	0.98	C7—H7	1
C2—H2B	0.98	C8—H8A	0.98
C2—H2C	0.98	C8—H8B	0.98
C3—H3A	0.98	C8—H8C	0.98
C3—H3B	0.98	C9—H9A	0.98
C3—H3C	0.98	C9—H9B	0.98
C4—C6	1.529 (3)	C9—H9C	0.98
Cl1^i—Pd1—Cl1	180.00 (3)	C6—C4—H4	105.2
Cl1^i—Pd1—P1	89.82 (2)	C5—C4—H4	105.2
Cl1—Pd1—P1	90.18 (2)	P1—C4—H4	105.2
Cl1^i—Pd1—P1^i	90.18 (2)	C4—C5—H5A	109.5
Cl1—Pd1—P1^i	89.82 (2)	C4—C5—H5B	109.5
P1—Pd1—P1^i	180	H5A—C5—H5B	109.5
C1—P1—C4	104.84 (11)	C4—C5—H5C	109.5
C1—P1—C7	104.47 (11)	H5A—C5—H5C	109.5
C4—P1—C7	110.77 (12)	H5B—C5—H5C	109.5
C1—P1—Pd1	109.81 (8)	C4—C6—H6A	109.5
C4—P1—Pd1	113.07 (8)	C4—C6—H6B	109.5
C7—P1—Pd1	113.18 (8)	H6A—C6—H6B	109.5
C3—C1—C2	110.7 (2)	C4—C6—H6C	109.5
C3—C1—P1	112.16 (17)	H6A—C6—H6C	109.5
C2—C1—P1	110.86 (17)	H6B—C6—H6C	109.5
C3—C1—H1	107.6	C8—C7—C9	110.8 (2)
C2—C1—H1	107.6	C8—C7—P1	116.30 (18)
P1—C1—H1	107.6	C9—C7—P1	111.43 (19)
C1—C2—H2A	109.5	C8—C7—H7	105.8
C1—C2—H2B	109.5	C9—C7—H7	105.8
H2A—C2—H2B	109.5	P1—C7—H7	105.8
C1—C2—H2C	109.5	C7—C8—H8A	109.5
H2A—C2—H2C	109.5	C7—C8—H8B	109.5
H2B—C2—H2C	109.5	H8A—C8—H8B	109.5
C1—C3—H3A	109.5	C7—C8—H8C	109.5
C1—C3—H3B	109.5	H8A—C8—H8C	109.5
H3A—C3—H3B	109.5	H8B—C8—H8C	109.5
C1—C3—H3C	109.5	C7—C9—H9A	109.5
H3A—C3—H3C	109.5	C7—C9—H9B	109.5
H3B—C3—H3C	109.5	H9A—C9—H9B	109.5
C6—C4—C5	110.8 (2)	C7—C9—H9C	109.5
C6—C4—P1	113.17 (18)	H9A—C9—H9C	109.5
C5—C4—P1	116.20 (17)	H9B—C9—H9C	109.5

Symmetry code: (i) −x+1, −y+1, −z.