New enanti­opure palladium(II) complexes from a stereodynamic 2,2'-biphosphole ligand

Two enantiopure palladium(II) complexes, viz. ­[1,1'-(butane-1,3-diyl)-3,3',4,4'-tetra­methyl-5,5'-diphenyl-2,2'-biphosphole]dichloridopalladium(II) dichloro­methane solvate [system­atic name: dichlorido(1,2,5,10,11-penta­methyl-3,9-diphenyl­perhydro­dicyclo­penta­[a,c][1,4]diphosphepine-[kappa]²P,P')palladium(II) dichloro­methane solvate], [PdCl₂(C₂₈H₃₀P₂)]·CH₂­Cl₂, have been synthesized from stereodynamic diphosphines derived from 2,2'-biphosphole through a metal kinetic dynamic resolution. In both structures, the coordination around the metal atom is square planar, with a cis arrangement of the ligands that drastically reduces the dihedral angle between the two phosphole rings compared with the free ligand. The structural determination of both enanti­omers unambiguously establishes the absolute configuration of both central and axial elements of chirality of the 2,2'-biphosphole framework and indicates that the original carbon chirality of the backbone controls the chiralities of the 2,2'-biphosphole framework.

S1. Comment

Considerable effort has been devoted to the design of new ligands for asymmetric catalysis (Ojima, 2000; Jacobsen et al., 1999; Noyori, 1994). Asymmetric catalysts are generally metal complexes with stereochemically rigid enantiopure ligands. However, stereochemically dynamic ligands can also be controlled into a single enantiomeric conformation on a metal centre and hence this methodology opens a new synthetic approach for the synthesis of enantiopure ligands (Walsh et al., 2003; Mikami, Aikawa, Yusa, Jodry & Yamanaka, 2002). Good results have been obtained with flexible diphosphines such as BIPHEP [Please define] (Mikami et al., 1999, 2004; Mikami, Aikawa, Yusa & Hatano, 2002; Becker et al., 2001), DPPF [Please define] (Mikami & Aikawa, 2002) and NUPHOS [Please define] (Doherty et al., 2005, 2004, 2003).

Recently, we reported the first application of chiral stereochemically dynamic 2,2'-biphosphole (BIPHOS) to asymmetric allylic substitution involving crystallization-induced spontaneous resolution and kinetic stabilization by coordination to a Pd centre (Tissot et al., 2001). The flexibility of 2,2'-biphosphole ligands is reflected in the configurational instability of the axial chirality generated by the 2,2'-biphosphole framework and the central chiralities at the P atoms (Tissot et al., 1996). In a more convenient procedure, we have discovered that dual chirality control can be achieved by introducing a chiral carbon linker between the two P atoms that favours a single enantiomeric form on a metal centre (Ortéga et al., 2003). The strategy used is based on a two-step chirality control process, involving firstly a partial chirality control in order to maintain some degree of freedom, and secondly a total chirality control by diastereoselective coordination on a metal centre (see reaction scheme).

By asymmetric alkylation of a 2,2'-biphospholyl dianion, (2), under highly dilute conditions, using various enantiomerically pure diol ditosylates or mesylates, an equilibrium mixture of diastereoisomeric diphosphines was obtained (Robé et al., 2005). The reaction of this equilibrium mixture with transition metals such as Pd, Pt and Rh resulted in dynamic resolution leading to diastereo- and enantiopure complexes. These enantiomeric Pd, Pt and Rh complexes can be used in asymmetric allylic alkylation (Robé et al., 2005), hydroformylation (Robé, Hegedüs, Bakos, Coppel et al., 2007) and hydrogenation (Robé, Hegedüs, Bakos, Daran & Gouygou, 2007), respectively.

We report here the structural characterization of two enantiomerically pure palladium complexes, (4), containing a diphosphine, (3), derived from 2,2'-biphosphole (see reaction scheme). Complexes (4a) and (4b) were obtained from diphosphines (3a) and (3b), respectively, which differ in the chirality of atom C1 within the backbone linking the two P atoms.

The unit cell and space group for (4a) and (4b) are identical, which agrees with the occurrence of the formation of two enantiomers. In both structures, the coordination around the metal is square-planar, with a cis arrangement of the ligands (Figs. 2 and 3). The refinement of the Flack parameter (Flack, 1983) clearly indicates that they are both enantiomerically pure in the solid state and that the absolute configuration is S[sp,Rp Rc] (axial chirality [phosphorus chirality, carbon chirality]) for (4a) and R[Rp,sp Sc] for (4b).

It is interesting to note that the ligand adopts a single configuration in these palladium complexes in which the two P atoms have opposite configurations, [sp,Rp] or [Rp,sp]. The coordination to Pd locks both the central and axial chirality of 2,2'-biphosphole, leading to drastically reduced P1—C11—C21—P2 torsion angles in complexes (4a) and (4b) compared with the BIPHOS ligand (Tissot et al., 1996) (Table 1).

These results prove unambiguously the influence of the chirality of the carbon backbone on the axial and central configuration of the 2,2'-biphosphole skeleton in complexes (4a) and (4b), as the (R) configuration provides the S[sp,Rp] configuration of (4a), whereas the (S) configuration leads to the R[Rp,sp] configuration of (4b).

The geometry of the chelating PdCl₂P₂(C₂)(C₃) framework is obviously identical within experimental error for (4a) and (4b) and closely related to the reported PdCl₂(BIPHOS) complex (Ortéga et al., 2003) containing a symmetrical chiral backbone (Table 1). This framework may be described in terms of the arrangement of the P1/C11/C21/P2, P1/C1/C2/P2 and P1/P2/Pd1/Cl1/Cl2 planes around the P1—P2 axes. The dihedral angles between these different planes are roughly identical in the three complexes (Table 1).

Related literature

For related literature, see: Becker et al. (2001); Doherty et al. (2003, 2004, 2005); Flack (1983); Jacobsen et al. (1999); Mikami & Aikawa (2002); Mikami et al. (1999, 2004); Mikami, Aikawa, Yusa & Hatano (2002); Mikami, Aikawa, Yusa, Jodry & Yamanaka (2002); Noyori (1994); Ojima (2000); Ortéga et al. (2003); Robé et al. (2005); Robé, Hegedüs, Bakos, Coppel, Daran & Gouygou (2007); Robé, Hegedüs, Bakos, Daran & Gouygou (2007); Tissot et al. (1996, 2001); Walsh et al. (2003).

S2. Experimental

Complexes (4a) and (4b) were synthesized according to a reported procedure (Robé et al., 2005) (see reaction scheme). Crystals suitable for X-ray analyses were obtained by slow evaporation of a CH₂Cl₂ solution. The enantiomers were separated by what means?

S3. Refinement

All H atoms were positioned geometrically and treated as riding, with C—H = 0.93 (aromatic), 0.96 (methyl) or 0.97 Å (methylene) and with U_iso(H) = 1.2U_eq(C_aromatic or C_methylene) or 1.5U_eq(C_methyl). Owing to the relatively poor quality of the data for (4b), the thermal displacement parameters for the C atoms were restrained using EADP constraints.

Computing details

For both compounds, 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: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. A molecular view of compound (4a), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity.
	Fig. 2. A molecular view of compound (4b), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity.

(4a) dichlorido(1,2,5,10,11-pentamethyl-3,9- diphenylperhydrodicyclopenta[a,c][1,4]diphosphepine-κ²P,P')palladium(II) dichloromethane solvate

Crystal data

[PdCl2(C28H30P2)]·CH2Cl2	F(000) = 700
Mr = 690.69	Dx = 1.551 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 4995 reflections
a = 8.9333 (4) Å	θ = 2.7–32.2°
b = 12.1598 (4) Å	µ = 1.12 mm^−1
c = 14.0088 (6) Å	T = 180 K
β = 103.678 (4)°	Needle, red
V = 1478.58 (10) Å^3	0.47 × 0.14 × 0.11 mm
Z = 2

Data collection

Oxford Diffraction Xcalibur diffractometer	4911 independent reflections
Radiation source: fine-focus sealed tube	4022 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
Detector resolution: 8.2632 pixels mm^-1	θmax = 26.4°, θmin = 2.5°
ω and ϕ scans	h = −10→11
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006) (empirical (using intensity measurements) absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm)	k = −15→13
Tmin = 0.597, Tmax = 0.885	l = −17→17
10919 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.051	H-atom parameters constrained
wR(F^2) = 0.143	w = 1/[σ^2(Fo^2) + (0.0885P)^2 + 0.9712P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.001
4911 reflections	Δρmax = 2.05 e Å^−3
330 parameters	Δρmin = −1.08 e Å^−3
1 restraint	Absolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.03 (5)

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	0.87403 (5)	0.38163 (5)	0.51128 (4)	0.02459 (16)
Cl1	0.8725 (2)	0.34940 (16)	0.67610 (13)	0.0347 (5)
Cl2	0.60521 (18)	0.3908 (2)	0.46057 (13)	0.0332 (4)
P1	0.9006 (2)	0.41117 (15)	0.35820 (14)	0.0252 (4)
P2	1.13145 (18)	0.37192 (19)	0.53132 (12)	0.0231 (4)
C1	0.9946 (9)	0.5450 (6)	0.3508 (6)	0.0294 (17)
H1	0.9102	0.5992	0.3260	0.035*
C2	1.2052 (10)	0.5091 (7)	0.5104 (6)	0.0336 (18)
H2A	1.2541	0.5425	0.5747	0.040*
H2B	1.2856	0.5009	0.4729	0.040*
C3	1.0820 (10)	0.5855 (7)	0.4553 (7)	0.0389 (19)
H3A	1.1299	0.6576	0.4483	0.047*
H3B	1.0057	0.5972	0.4953	0.047*
C4	1.0915 (12)	0.5441 (8)	0.2793 (7)	0.050 (2)
H4A	1.1228	0.6195	0.2686	0.074*
H4B	1.0329	0.5133	0.2170	0.074*
H4C	1.1832	0.4991	0.3046	0.074*
C11	1.0268 (9)	0.2997 (6)	0.3454 (6)	0.0316 (17)
C12	0.9536 (9)	0.2370 (6)	0.2676 (6)	0.0316 (17)
C13	0.8090 (9)	0.2846 (6)	0.2101 (6)	0.0306 (17)
C14	0.7613 (7)	0.3780 (9)	0.2467 (5)	0.0301 (14)
C21	1.1556 (9)	0.2870 (5)	0.4305 (5)	0.0260 (16)
C22	1.2838 (9)	0.2242 (6)	0.4581 (5)	0.0256 (15)
C23	1.3593 (8)	0.2392 (6)	0.5631 (6)	0.0274 (16)
C24	1.2915 (8)	0.3090 (6)	0.6160 (6)	0.0262 (16)
C121	0.9998 (10)	0.1230 (7)	0.2450 (7)	0.045 (2)
H12A	1.0610	0.1267	0.1955	0.067*
H12B	0.9073	0.0787	0.2196	0.067*
H12C	1.0613	0.0891	0.3050	0.067*
C131	0.7221 (11)	0.2288 (8)	0.1191 (6)	0.045 (2)
H13A	0.6668	0.1653	0.1369	0.068*
H13B	0.7942	0.2040	0.0807	0.068*
H13C	0.6481	0.2805	0.0800	0.068*
C141	0.6186 (9)	0.4411 (7)	0.2048 (6)	0.0335 (18)
C142	0.4786 (9)	0.3899 (10)	0.1943 (5)	0.0423 (19)
H142	0.4742	0.3169	0.2175	0.051*
C143	0.3423 (11)	0.4447 (10)	0.1497 (7)	0.050 (2)
H143	0.2455	0.4091	0.1419	0.060*
C144	0.3504 (12)	0.5507 (9)	0.1173 (7)	0.054 (3)
H144	0.2585	0.5880	0.0859	0.065*
C145	0.4884 (11)	0.6030 (8)	0.1295 (7)	0.049 (2)
H145	0.4915	0.6769	0.1083	0.059*
C146	0.6258 (11)	0.5487 (8)	0.1732 (7)	0.046 (2)
H146	0.7222	0.5849	0.1810	0.055*
C221	1.3547 (10)	0.1522 (7)	0.3957 (6)	0.0375 (19)
H22A	1.3339	0.0751	0.4083	0.056*
H22B	1.4662	0.1646	0.4111	0.056*
H22C	1.3108	0.1693	0.3263	0.056*
C231	1.5047 (9)	0.1766 (6)	0.6072 (6)	0.0316 (17)
H23A	1.5326	0.1880	0.6785	0.047*
H23B	1.5883	0.2030	0.5788	0.047*
H23C	1.4878	0.0980	0.5931	0.047*
C241	1.3557 (9)	0.3545 (6)	0.7140 (5)	0.0292 (17)
C242	1.2795 (9)	0.3535 (7)	0.7883 (6)	0.039 (2)
H242	1.1794	0.3222	0.7766	0.046*
C243	1.3447 (10)	0.3968 (10)	0.8794 (6)	0.049 (2)
H243	1.2929	0.3922	0.9313	0.059*
C244	1.4871 (12)	0.4472 (8)	0.8940 (7)	0.048 (2)
H244	1.5314	0.4794	0.9560	0.057*
C245	1.5649 (10)	0.4519 (8)	0.8222 (6)	0.041 (2)
H245	1.6619	0.4879	0.8334	0.049*
C246	1.5016 (9)	0.4035 (7)	0.7319 (6)	0.035 (2)
H246	1.5575	0.4037	0.6820	0.042*
C200	0.9295 (14)	0.3315 (10)	−0.0757 (8)	0.063 (3)
H20A	0.9563	0.3594	−0.1359	0.076*
H20B	0.8229	0.3028	−0.0947	0.076*
Cl21	0.9349 (4)	0.4392 (3)	0.0044 (2)	0.0767 (9)
Cl22	1.0525 (4)	0.2239 (3)	−0.0292 (3)	0.0729 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.0288 (3)	0.0148 (2)	0.0295 (3)	−0.0004 (2)	0.00544 (17)	−0.0008 (3)
Cl1	0.0410 (10)	0.0335 (12)	0.0295 (9)	−0.0030 (7)	0.0083 (7)	−0.0004 (7)
Cl2	0.0267 (8)	0.0294 (11)	0.0429 (9)	0.0004 (9)	0.0068 (6)	0.0000 (11)
P1	0.0301 (10)	0.0190 (11)	0.0262 (9)	0.0019 (7)	0.0062 (7)	0.0006 (7)
P2	0.0250 (8)	0.0155 (9)	0.0285 (8)	0.0003 (9)	0.0055 (6)	−0.0004 (9)
C1	0.038 (4)	0.015 (4)	0.033 (4)	−0.002 (3)	0.003 (3)	0.000 (3)
C2	0.043 (5)	0.019 (4)	0.034 (4)	−0.004 (3)	0.000 (4)	0.002 (3)
C3	0.054 (5)	0.015 (4)	0.047 (5)	−0.003 (3)	0.012 (4)	0.001 (4)
C4	0.071 (7)	0.030 (5)	0.045 (5)	−0.003 (4)	0.009 (5)	0.007 (4)
C11	0.043 (4)	0.013 (3)	0.037 (4)	0.004 (3)	0.003 (3)	0.005 (3)
C12	0.043 (4)	0.014 (4)	0.037 (4)	0.000 (3)	0.007 (3)	0.002 (3)
C13	0.032 (4)	0.023 (4)	0.035 (4)	−0.002 (3)	0.004 (3)	−0.004 (3)
C14	0.034 (3)	0.025 (3)	0.032 (3)	0.001 (4)	0.010 (3)	−0.006 (4)
C21	0.042 (4)	0.005 (3)	0.030 (4)	−0.004 (3)	0.006 (3)	0.000 (3)
C22	0.035 (4)	0.014 (3)	0.029 (4)	0.000 (3)	0.009 (3)	0.000 (3)
C23	0.031 (4)	0.010 (3)	0.044 (4)	0.006 (3)	0.013 (3)	0.004 (3)
C24	0.022 (4)	0.015 (3)	0.036 (4)	0.002 (3)	−0.003 (3)	0.008 (3)
C121	0.049 (5)	0.020 (4)	0.057 (6)	0.005 (4)	−0.004 (4)	−0.012 (4)
C131	0.055 (5)	0.037 (5)	0.035 (5)	−0.004 (4)	−0.006 (4)	−0.011 (4)
C141	0.043 (5)	0.030 (5)	0.024 (4)	0.004 (3)	0.001 (3)	−0.003 (3)
C142	0.047 (4)	0.044 (5)	0.033 (4)	0.000 (5)	0.004 (3)	0.014 (5)
C143	0.045 (5)	0.061 (7)	0.039 (5)	0.005 (5)	0.000 (4)	−0.004 (5)
C144	0.061 (6)	0.051 (6)	0.040 (5)	0.026 (5)	−0.010 (4)	−0.005 (5)
C145	0.062 (6)	0.034 (5)	0.042 (6)	0.016 (4)	−0.007 (4)	−0.003 (4)
C146	0.057 (6)	0.034 (5)	0.038 (5)	0.008 (4)	−0.004 (4)	0.001 (4)
C221	0.047 (5)	0.029 (5)	0.038 (5)	0.011 (4)	0.012 (4)	−0.003 (4)
C231	0.035 (4)	0.019 (4)	0.040 (5)	0.004 (3)	0.009 (3)	0.003 (3)
C241	0.034 (4)	0.020 (4)	0.029 (4)	0.004 (3)	−0.002 (3)	0.001 (3)
C242	0.037 (4)	0.046 (6)	0.031 (4)	−0.003 (3)	0.005 (3)	−0.005 (4)
C243	0.053 (5)	0.058 (7)	0.037 (4)	0.014 (5)	0.012 (4)	−0.003 (5)
C244	0.059 (6)	0.044 (6)	0.033 (5)	0.006 (4)	−0.005 (4)	−0.010 (4)
C245	0.035 (5)	0.039 (5)	0.043 (5)	−0.005 (4)	−0.001 (4)	−0.003 (4)
C246	0.041 (4)	0.032 (6)	0.029 (4)	−0.001 (3)	0.003 (3)	−0.001 (3)
C200	0.087 (8)	0.057 (7)	0.049 (6)	0.010 (6)	0.020 (6)	0.006 (5)
Cl21	0.087 (2)	0.0577 (18)	0.0673 (19)	0.0085 (15)	−0.0192 (15)	−0.0221 (14)
Cl22	0.084 (2)	0.0469 (17)	0.088 (2)	0.0038 (14)	0.0210 (16)	0.0042 (15)

Geometric parameters (Å, º)

Pd1—P1	2.2415 (19)	C121—H12C	0.9800
Pd1—P2	2.2529 (16)	C131—H13A	0.9800
Pd1—Cl2	2.3404 (16)	C131—H13B	0.9800
Pd1—Cl1	2.3452 (18)	C131—H13C	0.9800
P1—C14	1.797 (7)	C141—C142	1.374 (12)
P1—C11	1.799 (8)	C141—C146	1.388 (13)
P1—C1	1.845 (8)	C142—C143	1.398 (13)
P2—C24	1.798 (7)	C142—H142	0.9500
P2—C21	1.803 (8)	C143—C144	1.374 (16)
P2—C2	1.842 (8)	C143—H143	0.9500
C1—C4	1.470 (12)	C144—C145	1.361 (15)
C1—C3	1.568 (12)	C144—H144	0.9500
C1—H1	1.0000	C145—C146	1.401 (12)
C2—C3	1.506 (12)	C145—H145	0.9500
C2—H2A	0.9900	C146—H146	0.9500
C2—H2B	0.9900	C221—H22A	0.9800
C3—H3A	0.9900	C221—H22B	0.9800
C3—H3B	0.9900	C221—H22C	0.9800
C4—H4A	0.9800	C231—H23A	0.9800
C4—H4B	0.9800	C231—H23B	0.9800
C4—H4C	0.9800	C231—H23C	0.9800
C11—C12	1.364 (11)	C241—C242	1.371 (12)
C11—C21	1.456 (10)	C241—C246	1.401 (11)
C12—C13	1.469 (11)	C242—C243	1.377 (12)
C12—C121	1.501 (11)	C242—H242	0.9500
C13—C14	1.355 (12)	C243—C244	1.383 (14)
C13—C131	1.490 (11)	C243—H243	0.9500
C14—C141	1.485 (11)	C244—C245	1.352 (14)
C21—C22	1.355 (11)	C244—H244	0.9500
C22—C23	1.477 (11)	C245—C246	1.389 (11)
C22—C221	1.481 (10)	C245—H245	0.9500
C23—C24	1.360 (11)	C246—H246	0.9500
C23—C231	1.507 (10)	C200—Cl21	1.718 (12)
C24—C241	1.465 (10)	C200—Cl22	1.733 (12)
C121—H12A	0.9800	C200—H20A	0.9900
C121—H12B	0.9800	C200—H20B	0.9900
P1—Pd1—P2	77.99 (7)	C12—C121—H12A	109.5
P1—Pd1—Cl2	92.01 (7)	C12—C121—H12B	109.5
P2—Pd1—Cl2	169.80 (6)	H12A—C121—H12B	109.5
P1—Pd1—Cl1	174.41 (7)	C12—C121—H12C	109.5
P2—Pd1—Cl1	96.43 (7)	H12A—C121—H12C	109.5
Cl2—Pd1—Cl1	93.58 (7)	H12B—C121—H12C	109.5
C14—P1—C11	93.8 (4)	C13—C131—H13A	109.5
C14—P1—C1	112.3 (4)	C13—C131—H13B	109.5
C11—P1—C1	110.7 (4)	H13A—C131—H13B	109.5
C14—P1—Pd1	126.0 (3)	C13—C131—H13C	109.5
C11—P1—Pd1	100.7 (3)	H13A—C131—H13C	109.5
C1—P1—Pd1	110.4 (3)	H13B—C131—H13C	109.5
C24—P2—C21	92.8 (4)	C142—C141—C146	120.2 (8)
C24—P2—C2	103.4 (4)	C142—C141—C14	118.9 (9)
C21—P2—C2	106.3 (4)	C146—C141—C14	120.8 (8)
C24—P2—Pd1	137.1 (3)	C141—C142—C143	120.4 (10)
C21—P2—Pd1	103.9 (3)	C141—C142—H142	119.8
C2—P2—Pd1	109.0 (3)	C143—C142—H142	119.8
C4—C1—C3	113.3 (7)	C144—C143—C142	119.1 (10)
C4—C1—P1	112.4 (6)	C144—C143—H143	120.5
C3—C1—P1	110.9 (5)	C142—C143—H143	120.5
C4—C1—H1	106.6	C145—C144—C143	120.9 (9)
C3—C1—H1	106.6	C145—C144—H144	119.6
P1—C1—H1	106.6	C143—C144—H144	119.6
C3—C2—P2	113.2 (6)	C144—C145—C146	120.6 (10)
C3—C2—H2A	108.9	C144—C145—H145	119.7
P2—C2—H2A	108.9	C146—C145—H145	119.7
C3—C2—H2B	108.9	C141—C146—C145	118.8 (9)
P2—C2—H2B	108.9	C141—C146—H146	120.6
H2A—C2—H2B	107.7	C145—C146—H146	120.6
C2—C3—C1	115.3 (7)	C22—C221—H22A	109.5
C2—C3—H3A	108.5	C22—C221—H22B	109.5
C1—C3—H3A	108.5	H22A—C221—H22B	109.5
C2—C3—H3B	108.5	C22—C221—H22C	109.5
C1—C3—H3B	108.5	H22A—C221—H22C	109.5
H3A—C3—H3B	107.5	H22B—C221—H22C	109.5
C1—C4—H4A	109.5	C23—C231—H23A	109.5
C1—C4—H4B	109.5	C23—C231—H23B	109.5
H4A—C4—H4B	109.5	H23A—C231—H23B	109.5
C1—C4—H4C	109.5	C23—C231—H23C	109.5
H4A—C4—H4C	109.5	H23A—C231—H23C	109.5
H4B—C4—H4C	109.5	H23B—C231—H23C	109.5
C12—C11—C21	137.0 (7)	C242—C241—C246	118.4 (7)
C12—C11—P1	107.9 (6)	C242—C241—C24	123.6 (7)
C21—C11—P1	113.0 (6)	C246—C241—C24	118.0 (7)
C11—C12—C13	114.2 (7)	C241—C242—C243	121.6 (8)
C11—C12—C121	125.5 (7)	C241—C242—H242	119.2
C13—C12—C121	119.9 (7)	C243—C242—H242	119.2
C14—C13—C12	115.9 (7)	C242—C243—C244	118.6 (8)
C14—C13—C131	123.9 (7)	C242—C243—H243	120.7
C12—C13—C131	120.1 (7)	C244—C243—H243	120.7
C13—C14—C141	126.9 (7)	C245—C244—C243	121.7 (8)
C13—C14—P1	107.6 (6)	C245—C244—H244	119.1
C141—C14—P1	125.5 (7)	C243—C244—H244	119.1
C22—C21—C11	138.1 (7)	C244—C245—C246	119.3 (8)
C22—C21—P2	110.4 (5)	C244—C245—H245	120.3
C11—C21—P2	111.3 (6)	C246—C245—H245	120.3
C21—C22—C23	111.7 (6)	C245—C246—C241	120.2 (8)
C21—C22—C221	128.0 (7)	C245—C246—H246	119.9
C23—C22—C221	120.2 (6)	C241—C246—H246	119.9
C24—C23—C22	117.6 (6)	Cl21—C200—Cl22	114.4 (6)
C24—C23—C231	122.9 (7)	Cl21—C200—H20A	108.7
C22—C23—C231	119.5 (6)	Cl22—C200—H20A	108.7
C23—C24—C241	128.3 (7)	Cl21—C200—H20B	108.7
C23—C24—P2	107.0 (6)	Cl22—C200—H20B	108.7
C241—C24—P2	122.1 (5)	H20A—C200—H20B	107.6
C12—C11—C21—C22	23.0 (18)	P1—C11—C21—P2	9.8 (7)

(4b) dichlorido(1,2,5,10,11-pentamethyl-3,9- diphenylperhydrodicyclopenta[a,c][1,4]diphosphepine-κ²P,P')palladium(II) dichloromethane solvate

Crystal data

[PdCl2(C28H30P2)]·CH2Cl2	F(000) = 700
Mr = 690.69	Dx = 1.552 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1192 reflections
a = 8.963 (3) Å	θ = 2.9–32.0°
b = 12.139 (5) Å	µ = 1.12 mm^−1
c = 13.989 (6) Å	T = 180 K
β = 103.87 (3)°	Box, red
V = 1477.6 (10) Å^3	0.38 × 0.24 × 0.21 mm
Z = 2

Data collection

Oxford Diffraction Xcalibur diffractometer	4033 independent reflections
Radiation source: fine-focus sealed tube	1900 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.079
Detector resolution: 8.2632 pixels mm^-1	θmax = 25.0°, θmin = 2.9°
ω and ϕ scans	h = −7→10
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006) (empirical (using intensity measurements) absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm)	k = −14→14
Tmin = 0.688, Tmax = 0.791	l = −15→16
5431 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.080	H-atom parameters constrained
wR(F^2) = 0.226	w = 1/[σ^2(Fo^2) + (0.0951P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.97	(Δ/σ)max = 0.003
4033 reflections	Δρmax = 1.66 e Å^−3
168 parameters	Δρmin = −1.30 e Å^−3
13 restraints	Absolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.02 (11)

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	−0.12540 (17)	0.30787 (17)	0.51225 (9)	0.0231 (4)
Cl1	−0.1251 (6)	0.3397 (4)	0.6772 (3)	0.0351 (17)
Cl2	−0.3941 (5)	0.2977 (6)	0.4621 (3)	0.0278 (13)
P1	−0.0991 (6)	0.2789 (4)	0.3590 (3)	0.0254 (16)
P2	0.1327 (5)	0.3167 (6)	0.5329 (3)	0.0218 (12)
C1	−0.013 (2)	0.1429 (17)	0.3471 (13)	0.0326 (14)
H1	−0.0961	0.0898	0.3239	0.039*
C2	0.215 (2)	0.1778 (17)	0.5139 (13)	0.0326 (14)
H2A	0.2929	0.1866	0.4769	0.039*
H2B	0.2636	0.1459	0.5774	0.039*
C3	0.091 (2)	0.1015 (17)	0.4593 (13)	0.0326 (14)
H3A	0.0206	0.0880	0.5007	0.039*
H3B	0.1391	0.0316	0.4509	0.039*
C4	0.090 (2)	0.1430 (17)	0.2757 (13)	0.0326 (14)
H4A	0.1947	0.1557	0.3110	0.049*
H4B	0.0584	0.2003	0.2278	0.049*
H4C	0.0832	0.0730	0.2429	0.049*
C11	0.025 (2)	0.3926 (17)	0.3450 (13)	0.0326 (14)
C12	−0.047 (2)	0.4488 (17)	0.2694 (13)	0.0326 (14)
C13	−0.181 (2)	0.4055 (17)	0.2132 (13)	0.0326 (14)
C14	−0.241 (2)	0.303 (2)	0.2444 (11)	0.0326 (14)
C21	0.151 (2)	0.4048 (17)	0.4329 (13)	0.0326 (14)
C22	0.290 (2)	0.4661 (17)	0.4613 (13)	0.0326 (14)
C23	0.368 (2)	0.4502 (17)	0.5656 (13)	0.0326 (14)
C24	0.303 (2)	0.3778 (18)	0.6180 (13)	0.0326 (14)
C121	−0.012 (2)	0.5602 (16)	0.2397 (13)	0.0326 (14)
H12A	−0.0993	0.6073	0.2371	0.049*
H12B	0.0096	0.5572	0.1758	0.049*
H12C	0.0753	0.5889	0.2866	0.049*
C131	−0.278 (2)	0.4694 (17)	0.1215 (12)	0.0326 (14)
H13A	−0.3011	0.5418	0.1412	0.049*
H13B	−0.3713	0.4303	0.0946	0.049*
H13C	−0.2190	0.4752	0.0725	0.049*
C141	−0.372 (2)	0.2452 (13)	0.2074 (13)	0.0326 (14)
C142	−0.366 (2)	0.1363 (13)	0.1756 (12)	0.0326 (14)
H142	−0.2736	0.0982	0.1825	0.039*
C143	−0.5108 (18)	0.0886 (17)	0.1321 (13)	0.0414 (17)
H143	−0.5079	0.0159	0.1117	0.050*
C144	−0.659 (2)	0.1357 (14)	0.1153 (14)	0.0414 (17)
H144	−0.7488	0.0992	0.0837	0.050*
C145	−0.656 (2)	0.2430 (14)	0.1514 (13)	0.0414 (17)
H145	−0.7486	0.2802	0.1466	0.050*
C146	−0.5162 (17)	0.2963 (19)	0.1952 (11)	0.0414 (17)
H146	−0.5196	0.3685	0.2170	0.050*
C221	0.365 (2)	0.5386 (19)	0.4006 (13)	0.0414 (17)
H22A	0.3180	0.5271	0.3321	0.062*
H22B	0.4723	0.5211	0.4134	0.062*
H22C	0.3528	0.6143	0.4173	0.062*
C231	0.496 (2)	0.5056 (19)	0.6045 (13)	0.0414 (17)
H23A	0.5232	0.4947	0.6745	0.062*
H23B	0.4792	0.5826	0.5904	0.062*
H23C	0.5776	0.4796	0.5768	0.062*
C241	0.354 (2)	0.3347 (18)	0.7130 (12)	0.0414 (17)
C242	0.273 (2)	0.3307 (18)	0.7864 (10)	0.0414 (17)
H242	0.1739	0.3593	0.7731	0.050*
C243	0.334 (2)	0.2856 (17)	0.8788 (11)	0.0414 (17)
H243	0.2796	0.2825	0.9274	0.050*
C244	0.482 (2)	0.2459 (18)	0.8932 (13)	0.0414 (17)
H244	0.5301	0.2204	0.9557	0.050*
C245	0.565 (2)	0.2412 (17)	0.8205 (10)	0.0414 (17)
H245	0.6603	0.2072	0.8323	0.050*
C246	0.499 (2)	0.2893 (17)	0.7295 (11)	0.0414 (17)
H246	0.5525	0.2908	0.6803	0.050*
C100	−0.041 (3)	0.3599 (19)	−0.0763 (14)	0.0414 (17)
H10A	0.0107	0.3290	−0.1239	0.050*
H10B	−0.1420	0.3834	−0.1123	0.050*
Cl3	−0.0634 (10)	0.2539 (7)	0.0054 (5)	0.095 (3)
Cl4	0.0524 (9)	0.4657 (7)	−0.0290 (6)	0.085 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.0243 (9)	0.0167 (8)	0.0300 (7)	0.0006 (10)	0.0095 (5)	−0.0001 (9)
Cl1	0.038 (4)	0.042 (5)	0.028 (3)	0.013 (3)	0.014 (2)	0.003 (2)
Cl2	0.022 (3)	0.026 (3)	0.037 (3)	−0.001 (3)	0.010 (2)	−0.003 (3)
P1	0.024 (3)	0.026 (5)	0.025 (3)	0.003 (3)	0.005 (2)	0.003 (2)
P2	0.021 (3)	0.014 (3)	0.027 (2)	−0.009 (3)	0.0001 (19)	−0.008 (3)
C1	0.040 (4)	0.027 (3)	0.027 (3)	−0.002 (3)	0.002 (2)	−0.001 (2)
C2	0.040 (4)	0.027 (3)	0.027 (3)	−0.002 (3)	0.002 (2)	−0.001 (2)
C3	0.040 (4)	0.027 (3)	0.027 (3)	−0.002 (3)	0.002 (2)	−0.001 (2)
C4	0.040 (4)	0.027 (3)	0.027 (3)	−0.002 (3)	0.002 (2)	−0.001 (2)
C11	0.040 (4)	0.027 (3)	0.027 (3)	−0.002 (3)	0.002 (2)	−0.001 (2)
C12	0.040 (4)	0.027 (3)	0.027 (3)	−0.002 (3)	0.002 (2)	−0.001 (2)
C13	0.040 (4)	0.027 (3)	0.027 (3)	−0.002 (3)	0.002 (2)	−0.001 (2)
C14	0.040 (4)	0.027 (3)	0.027 (3)	−0.002 (3)	0.002 (2)	−0.001 (2)
C21	0.040 (4)	0.027 (3)	0.027 (3)	−0.002 (3)	0.002 (2)	−0.001 (2)
C22	0.040 (4)	0.027 (3)	0.027 (3)	−0.002 (3)	0.002 (2)	−0.001 (2)
C23	0.040 (4)	0.027 (3)	0.027 (3)	−0.002 (3)	0.002 (2)	−0.001 (2)
C24	0.040 (4)	0.027 (3)	0.027 (3)	−0.002 (3)	0.002 (2)	−0.001 (2)
C121	0.040 (4)	0.027 (3)	0.027 (3)	−0.002 (3)	0.002 (2)	−0.001 (2)
C131	0.040 (4)	0.027 (3)	0.027 (3)	−0.002 (3)	0.002 (2)	−0.001 (2)
C141	0.040 (4)	0.027 (3)	0.027 (3)	−0.002 (3)	0.002 (2)	−0.001 (2)
C142	0.040 (4)	0.027 (3)	0.027 (3)	−0.002 (3)	0.002 (2)	−0.001 (2)
C143	0.045 (4)	0.048 (4)	0.031 (3)	−0.003 (3)	0.008 (3)	0.007 (3)
C144	0.045 (4)	0.048 (4)	0.031 (3)	−0.003 (3)	0.008 (3)	0.007 (3)
C145	0.045 (4)	0.048 (4)	0.031 (3)	−0.003 (3)	0.008 (3)	0.007 (3)
C146	0.045 (4)	0.048 (4)	0.031 (3)	−0.003 (3)	0.008 (3)	0.007 (3)
C221	0.045 (4)	0.048 (4)	0.031 (3)	−0.003 (3)	0.008 (3)	0.007 (3)
C231	0.045 (4)	0.048 (4)	0.031 (3)	−0.003 (3)	0.008 (3)	0.007 (3)
C241	0.045 (4)	0.048 (4)	0.031 (3)	−0.003 (3)	0.008 (3)	0.007 (3)
C242	0.045 (4)	0.048 (4)	0.031 (3)	−0.003 (3)	0.008 (3)	0.007 (3)
C243	0.045 (4)	0.048 (4)	0.031 (3)	−0.003 (3)	0.008 (3)	0.007 (3)
C244	0.045 (4)	0.048 (4)	0.031 (3)	−0.003 (3)	0.008 (3)	0.007 (3)
C245	0.045 (4)	0.048 (4)	0.031 (3)	−0.003 (3)	0.008 (3)	0.007 (3)
C246	0.045 (4)	0.048 (4)	0.031 (3)	−0.003 (3)	0.008 (3)	0.007 (3)
C100	0.045 (4)	0.048 (4)	0.031 (3)	−0.003 (3)	0.008 (3)	0.007 (3)
Cl3	0.111 (7)	0.075 (6)	0.080 (5)	0.010 (5)	−0.017 (5)	0.026 (4)
Cl4	0.080 (7)	0.066 (6)	0.107 (6)	−0.006 (5)	0.015 (5)	−0.008 (4)

Geometric parameters (Å, º)

Pd1—P1	2.239 (5)	C121—H12C	0.9600
Pd1—P2	2.264 (5)	C131—H13A	0.9600
Pd1—Cl1	2.339 (5)	C131—H13B	0.9600
Pd1—Cl2	2.345 (5)	C131—H13C	0.9600
P1—C14	1.814 (16)	C141—C142	1.401 (10)
P1—C11	1.82 (2)	C141—C146	1.406 (10)
P1—C1	1.85 (2)	C142—C143	1.421 (9)
P2—C21	1.80 (2)	C142—H142	0.9300
P2—C24	1.85 (2)	C143—C144	1.415 (10)
P2—C2	1.89 (2)	C143—H143	0.9300
C1—C4	1.52 (3)	C144—C145	1.395 (10)
C1—C3	1.70 (3)	C144—H144	0.9300
C1—H1	0.9800	C145—C146	1.417 (10)
C2—C3	1.51 (3)	C145—H145	0.9300
C2—H2A	0.9700	C146—H146	0.9300
C2—H2B	0.9700	C221—H22A	0.9600
C3—H3A	0.9700	C221—H22B	0.9600
C3—H3B	0.9700	C221—H22C	0.9600
C4—H4A	0.9600	C231—H23A	0.9600
C4—H4B	0.9600	C231—H23B	0.9600
C4—H4C	0.9600	C231—H23C	0.9600
C11—C12	1.29 (2)	C241—C246	1.381 (9)
C11—C21	1.46 (2)	C241—C242	1.391 (9)
C12—C13	1.38 (3)	C242—C243	1.389 (9)
C12—C121	1.47 (3)	C242—H242	0.9300
C13—C14	1.46 (3)	C243—C244	1.378 (9)
C13—C131	1.57 (2)	C243—H243	0.9300
C14—C141	1.36 (3)	C244—C245	1.395 (10)
C21—C22	1.42 (3)	C244—H244	0.9300
C22—C23	1.47 (3)	C245—C246	1.396 (9)
C22—C221	1.49 (3)	C245—H245	0.9300
C23—C231	1.32 (3)	C246—H246	0.9300
C23—C24	1.37 (3)	C100—Cl4	1.59 (2)
C24—C241	1.40 (2)	C100—Cl3	1.77 (2)
C121—H12A	0.9600	C100—H10A	0.9700
C121—H12B	0.9600	C100—H10B	0.9700
P1—Pd1—P2	77.94 (19)	C12—C121—H12A	109.5
P1—Pd1—Cl1	174.0 (2)	C12—C121—H12B	109.5
P2—Pd1—Cl1	96.11 (18)	H12A—C121—H12B	109.5
P1—Pd1—Cl2	92.39 (18)	C12—C121—H12C	109.5
P2—Pd1—Cl2	170.24 (17)	H12A—C121—H12C	109.5
Cl1—Pd1—Cl2	93.56 (17)	H12B—C121—H12C	109.5
C14—P1—C11	95.7 (10)	C13—C131—H13A	109.5
C14—P1—C1	106.5 (10)	C13—C131—H13B	109.5
C11—P1—C1	112.9 (10)	H13A—C131—H13B	109.5
C14—P1—Pd1	127.5 (7)	C13—C131—H13C	109.5
C11—P1—Pd1	101.1 (6)	H13A—C131—H13C	109.5
C1—P1—Pd1	111.6 (6)	H13B—C131—H13C	109.5
C21—P2—C24	92.7 (9)	C14—C141—C142	120.6 (17)
C21—P2—C2	108.1 (9)	C14—C141—C146	120.3 (17)
C24—P2—C2	99.1 (9)	C142—C141—C146	119.0 (19)
C21—P2—Pd1	102.1 (7)	C141—C142—C143	114.6 (18)
C24—P2—Pd1	139.5 (7)	C141—C142—H142	122.7
C2—P2—Pd1	111.2 (7)	C143—C142—H142	122.7
C4—C1—C3	108.7 (17)	C144—C143—C142	129 (2)
C4—C1—P1	113.2 (14)	C144—C143—H143	115.3
C3—C1—P1	109.3 (13)	C142—C143—H143	115.3
C4—C1—H1	108.5	C145—C144—C143	112 (2)
C3—C1—H1	108.5	C145—C144—H144	123.8
P1—C1—H1	108.5	C143—C144—H144	123.8
C3—C2—P2	110.9 (15)	C144—C145—C146	121 (2)
C3—C2—H2A	109.5	C144—C145—H145	119.3
P2—C2—H2A	109.5	C146—C145—H145	119.3
C3—C2—H2B	109.5	C141—C146—C145	123 (2)
P2—C2—H2B	109.5	C141—C146—H146	118.5
H2A—C2—H2B	108.0	C145—C146—H146	118.5
C2—C3—C1	117.5 (16)	C22—C221—H22A	109.5
C2—C3—H3A	107.9	C22—C221—H22B	109.5
C1—C3—H3A	107.9	H22A—C221—H22B	109.5
C2—C3—H3B	107.9	C22—C221—H22C	109.5
C1—C3—H3B	107.9	H22A—C221—H22C	109.5
H3A—C3—H3B	107.2	H22B—C221—H22C	109.5
C1—C4—H4A	109.5	C23—C231—H23A	109.5
C1—C4—H4B	109.5	C23—C231—H23B	109.5
H4A—C4—H4B	109.5	H23A—C231—H23B	109.5
C1—C4—H4C	109.5	C23—C231—H23C	109.5
H4A—C4—H4C	109.5	H23A—C231—H23C	109.5
H4B—C4—H4C	109.5	H23B—C231—H23C	109.5
C12—C11—C21	140 (2)	C246—C241—C242	119.9 (17)
C12—C11—P1	106.7 (16)	C246—C241—C24	112.7 (14)
C21—C11—P1	110.8 (14)	C242—C241—C24	127.3 (17)
C11—C12—C13	118 (2)	C243—C242—C241	122.7 (17)
C11—C12—C121	128.1 (19)	C243—C242—H242	118.6
C13—C12—C121	113.9 (17)	C241—C242—H242	118.6
C12—C13—C14	119.1 (17)	C244—C243—C242	115.2 (17)
C12—C13—C131	120.9 (18)	C244—C243—H243	122.4
C14—C13—C131	119.9 (17)	C242—C243—H243	122.4
C141—C14—C13	132.0 (17)	C243—C244—C245	124.5 (18)
C141—C14—P1	127.6 (17)	C243—C244—H244	117.7
C13—C14—P1	100.1 (13)	C245—C244—H244	117.7
C22—C21—C11	137.2 (19)	C244—C245—C246	117.8 (18)
C22—C21—P2	109.3 (13)	C244—C245—H245	121.1
C11—C21—P2	113.5 (16)	C246—C245—H245	121.1
C21—C22—C23	112.9 (17)	C241—C246—C245	119.6 (17)
C21—C22—C221	129.4 (17)	C241—C246—H246	120.2
C23—C22—C221	117.8 (18)	C245—C246—H246	120.2
C231—C23—C24	123.1 (18)	Cl4—C100—Cl3	116.7 (12)
C231—C23—C22	120.1 (19)	Cl4—C100—H10A	108.1
C24—C23—C22	116.7 (19)	Cl3—C100—H10A	108.1
C23—C24—C241	131.8 (19)	Cl4—C100—H10B	108.1
C23—C24—P2	107.9 (14)	Cl3—C100—H10B	108.1
C241—C24—P2	119.4 (15)	H10A—C100—H10B	107.3
P1—C11—C21—P2	−7 (2)