Acetonitrile­[2-({bis[2,4,6-tris­(trifluorido­meth­yl)phen­yl]phosphan­yloxy}meth­yl)pyridine]­meth­ylpalladium(II) hexa­fluoro­anti­monate dichloro­methane hemisolvate

Liuzhong Li; Peter S White; Aiyou Hao

doi:10.1107/S1600536811005757

. 2011 Feb 23;67(Pt 3):m366. doi: 10.1107/S1600536811005757

Acetonitrile[2-({bis[2,4,6-tris(trifluoridomethyl)phenyl]phosphanyloxy}methyl)pyridine]methylpalladium(II) hexafluoroantimonate dichloromethane hemisolvate

Liuzhong Li ^a,^b, Peter S White ^b, Aiyou Hao ^a,^*

PMCID: PMC3051961 PMID: 21522290

Abstract

In the title compound, [Pd(CH₃)(C₂₄H₁₀F₁₈NOP)(CH₃CN)][SbF₆]·0.5CH₂Cl₂, the Pd^II atom has a distorted square-planar environment being coordinated by an acetonitrile N atom [Pd—N = 2.079 (3) Å], a methyl C atom [Pd—C = 2.047 (4) Å] and the bidentate ligand 2-({[2,4,6-tris(trifluoromethyl)phenyl]phosphanyloxy}methyl)pyridine (L). In L, the short distance of 3.621 (3) Å between the centroids of pyridine and benzene rings indicates the presence of a π–π interaction. The crystal packing exhibits weak intermolecular C—H⋯F contacts. The solvent molecule has been treated as disordered between two positions of equal occupancy related by an inversion center.

Related literature

For related compounds, see: Li et al. (2011 ▶) and references therein. Di[tris(trifluoromethyl)phenyl]phosphine chloride was prepared according to Batsanov et al. (2002 ▶).

Experimental

Crystal data

[Pd(CH₃)(C₂₄H₁₀F₁₈NOP)(C₂H₃N)][SbF₆]·0.5CH₂Cl₂
M _r = 1142.00
Triclinic,
a = 8.6993 (4) Å
b = 11.8120 (5) Å
c = 18.1494 (8) Å
α = 78.557 (2)°
β = 82.007 (2)°
γ = 79.526 (2)°
V = 1787.14 (14) Å³
Z = 2
Cu Kα radiation
μ = 12.64 mm⁻¹
T = 100 K
0.38 × 0.13 × 0.11 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: numerical (SADABS; Bruker, 2007 ▶) T _min = 0.086, T _max = 0.348
19130 measured reflections
6422 independent reflections
5830 reflections with I > 2σ(I)
R _int = 0.035

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.093
S = 1.05
6422 reflections
534 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 1.46 e Å⁻³
Δρ_min = −0.88 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811005757/cv5046sup1.cif

e-67-0m366-sup1.cif^{(30.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811005757/cv5046Isup2.hkl

e-67-0m366-Isup2.hkl^{(314.3KB, 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
C4—H4C⋯F16ⁱ	0.98	2.44	3.310 (10)	148
C11—H11B⋯F11	0.99	2.58	3.489 (9)	154
C9—H9⋯F11	0.95	2.47	3.345 (9)	152

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Symmetry code: (i) Inline graphic .

Acknowledgments

We thank Professor Maurice S. Brookhart for helpful discussions.

supplementary crystallographic information

Comment

In continuation of our structural study of Pd complexes with phosphine-imine ligands (Li et al., 2011), we present here the title compound (I). In (I) (Fig. 1), each Pd center has a distorted square-planar environment being coordinated by acetonitrile [Pd—N 2.079 (3) Å], methyl [Pd—C 2.047 (4) Å] and bidentate ligand L. The solvent molecule has been treated as disordered between two positions related by inversion center with occupancies fixed to 0.5 each. The crystal packing exhibits weak intermolecular C—H···F contacts (Table 1).

Experimental

All manipulations of air- and/or moisture-sensitive compounds were conducted using standard Schlenk techniques. Argon was purified by passage through columns of BASF R3–11 catalyst (Chemalog) and 4Å molecular sieves. All solvents were deoxygenated, dried and distilled using common techniques. Di[tris(trifluoromethyl)phenyl]phosphine chloride were prepared according to the literature procedures(Batsanov et al., 2002). A flame-dried Schlenk flask was charged with purified 2-pyridyl-carbinal (138 mg, 1.27 mmol) and dried THF (5 ml). The solution was cooled to -78°C and stirred for 30 min, 1.6 mol/l n-BuLi in hexane (0.8 ml, 1.28 mmol) was added slowly. After stirring of 1.0 hrs at -78°C, 800 mg of di[tris(trifluoromethyl)phenyl]phosphine chloride in THF(2 ml) was added slowly. Stirring for 1 day at -78°C, and brought it to room temperature and stirred overnight. 3.0 ml degassed saturated NaCl solution was charged for hydrolysis. After separation, dry and column purification, the ligand of 2- methoxy(di(2,4,6-tris(trifluoromethyl) phenyl)phosphino)] pyridine(0.45 g) was obtained. The yield is 50%. The neutral complex was prepared by reaction of the above ligand (1.0 equiv.) and (COD)PdMeCl (1.0 equiv.) at RT, and the cationic complex was obtained by reacting the neutral complex(1.0 equiv) with AgSbF₆ (1.0 equiv.) at RT. Single crystal of the cationic complex was cultivated by recrystallization of CH₂Cl₂ and pentane. Anal. Calcd for C27H16F24N2OPPdSb: C, 29.49; H, 1.47; N, 2.55. Found: C, 29.52; H, 1.30; N, 2.27.