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Acta Cryst. (2007). E63, m3086    [ doi:10.1107/S1600536807059405 ]

Bis[2,6-bis(dipiperidin-1-ylphosphanyloxy)phenyl]bromidopalladium(II)

J. L. Bolliger, O. Blacque and C. M. Frech

Abstract top

The title compound, [PdBr(C26H43N4O2P2)], a so-called palladium pincer complex, is a very efficient catalyst for the Suzuki cross-coupling reaction. The Pd atom exhibits a distorted square-planar coordination, typical for PdII complexes.

Comment top

In a recent article, we reported a new concept for the synthesis of aminophosphine-based pincer complexes of palladium with the general formula of [Pd(Cl){C6H3(XP(piperidinyl)2)2}] (X = NH or O), which were formed by facile activation of C—H and P—N bonds (Bolliger et al., 2007). These complexes proved to be extremely efficient catalysts for the Suzuki–Miyaura cross-coupling reaction (Miyaura et al., 1979) and led to very high conversion rates and quantitative yields in extremely short reaction times and with very low catalyst loadings. The analogous bromo complex [Pd(Br){C6H3(OP(piperidinyl)2)2}] (I), which was found to be formed in the catalytic cycle, was independently prepared and the x-ray structure is presented here.

The crystal structure of (I) consists of discrete molecules with no intermolecular short contacts. The palladium atom presents a distorted square planar coordination with Br, C1, P1 and P2 as donor atoms. The main distortion affects the angle P—Pd—P of the mutually trans phosphorus atoms (160.31 (3)°) and is a consequence of the two five-membered rings which impose strains to the coordination sphere. The Pd—Br bond length of 2.5066 (7) Å is very similar to values found in the literature for the [Pd(Br){C6H3(XPR2)2}] compounds: 2.495 (1) Å, X = CH2, R = Ph (Bachechi, 2003) and 2.514 (2) Å, X = CH2, R = Cy (Cross et al., 1995). The Pd—P bond distances of 2.2808 (7) and 2.2891 (7) Å fall in the typical range observed for compounds with the [Pd{C6H3(XPR2)2}] moiety.

Related literature top

For related literature, see: Bolliger et al. (2007); Miyaura et al. (1979); Bachechi (2003); Cross et al. (1995).

Experimental top

To an orange suspension of 0.709 g (1.89 mmol) of [Pd(Br)2(cod)] (cod=cycloocta-1,5-diene) in 15 ml of tetrahydrofurane, 1.077 g (3.80 mmol, 2.01 equiv.) of P(NC5H10)3 (dissolved in 10 ml of tetrahydrofurane) was added and stirred for 5 minutes at room temperature, which quantitatively yielded the dibromo-(bis(1,1',1''-(phosphinetriyl)tripiperidine))palladium [Pd(Br)2{P(NC5H10)3}2] complex. To a toluene solution (10 ml) of 262.8 mg (0.32 mmol) of [Pd(Br)2{P(NC5H10)3}2], 36.0 mg (0.33 mmol, 1.01 equiv.) of resorcinol was added. The reaction mixture was placed in an oil bath and heated up to 80°C for 15 minutes, during which the solution decolorized. The solvent was removed under reduced pressure, and the solid was extracted with 20 ml of diethyl ether. After removal of the solvent in vacuo, 161.5 mg (0.24 mmol, 74%) of [Pd(Br){C6H3(OP(piperidinyl)2)2}] (I) was obtained as colorless powder.

Colorless crystals of the title compound (I) were obtained by slow evaporation of the solvent from a saturated diethyl ether solution at room temperature within three weeks.

31P{1H}-NMR (C6D6; δ, p.p.m.): 147.6 (s, P(NC5H10)2).

1H NMR (C6D6; δ,p.p.m.): 6.96 (t, 3JHH = 8.0 Hz, 1H, Arpara), 6.63 (d, 3JHH = 8.0 Hz, 2H, Armeta), 3.27 (m, 16H, NCH2), 1.41 (m, 16H, NCH2CH2),1.27 (m, 8H, NCH2CH2CH2).

13C{1H} NMR (C6D6; δ, p.p.m.): 160.9 (vt, JPC = 10.2 Hz, ArOP), 129.3 (s, Arpara), 126.9 (unresolved t, Aripso), 106.4 (vt, JPC = 8.4 Hz, Armeta), 46.7 (vt, 2JPC = 4JPC = 4.1, NCH2), 26.6 (s, NCH2CH2), 24.9 (s, NCH2CH2CH2). The assignmentof the 1H and 13C{1H} NMR signals was confirmed by COSY and 13C{1H}DEPT experiments.

Elemental Analysis: Calc. for C26H43BrN4O2P2Pd: C, 45.13; H, 6.26; N, 8.10. Found: C, 45.08; H, 6.35; N, 8.13.

Refinement top

All hydrogen atoms were included at calculated positions and treated as riding atoms with C—H distances of 0.93–0.97 Å and Uiso(H) = 1.3Ueq(C)].

Computing details top

Data collection: IPDS Software (Stoe & Cie, 1999); cell refinement: IPDS Software (Stoe & Cie, 1999); data reduction: IPDS Software (Stoe & Cie, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); 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) and SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) with the atom-labeling scheme (30% probability displacement ellipsoids).
Bis[2,6-bis(dipiperidin-1-ylphosphanyloxy)phenyl]bromidopalladium(II) top
Crystal data top
[PdBr(C26H43N4O2P2)]Z = 2
Mr = 691.9F000 = 708
Triclinic, P1Dx = 1.522 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 9.8843 (15) ÅCell parameters from 8000 reflections
b = 12.3457 (19) Åθ = 3.1–30.2º
c = 13.815 (2) ŵ = 2.07 mm−1
α = 76.635 (18)ºT = 183 (2) K
β = 70.676 (17)ºPlate, colourless
γ = 73.847 (17)º0.33 × 0.32 × 0.12 mm
V = 1510.0 (4) Å3
Data collection top
Stoe IPDS
diffractometer		Rint = 0.056
φ oscillation scansθmax = 25º
Absorption correction: numerical
(Coppens et al., 1965)		θmin = 3.1º
Tmin = 0.568, Tmax = 0.797h = −11→11
19696 measured reflectionsk = −14→14
4989 independent reflectionsl = −16→16
4431 reflections with I > 2σ(I)
Refinement top
Refinement on F2H-atom parameters constrained
Least-squares matrix: full  w = 1/[σ2(Fo2) + (0.0407P)2 + 0.1788P]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.024(Δ/σ)max = 0.001
wR(F2) = 0.065Δρmax = 0.71 e Å−3
S = 1.02Δρmin = −0.36 e Å−3
4989 reflectionsExtinction correction: none
325 parameters
Crystal data top
[PdBr(C26H43N4O2P2)]γ = 73.847 (17)º
Mr = 691.9V = 1510.0 (4) Å3
Triclinic, P1Z = 2
a = 9.8843 (15) ÅMo Kα
b = 12.3457 (19) ŵ = 2.07 mm−1
c = 13.815 (2) ÅT = 183 (2) K
α = 76.635 (18)º0.33 × 0.32 × 0.12 mm
β = 70.676 (17)º
Data collection top
Stoe IPDS
diffractometer		4989 independent reflections
Absorption correction: numerical
(Coppens et al., 1965)		4431 reflections with I > 2σ(I)
Tmin = 0.568, Tmax = 0.797Rint = 0.056
19696 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.024325 parameters
wR(F2) = 0.065H-atom parameters constrained
S = 1.02Δρmax = 0.71 e Å−3
4989 reflectionsΔρmin = −0.36 e Å−3
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Pd10.595039 (18)0.296726 (15)0.253679 (13)0.02177 (7)
Br10.37214 (3)0.32621 (3)0.40672 (2)0.03958 (9)
P10.59392 (7)0.11866 (5)0.23383 (5)0.02443 (14)
P20.67472 (7)0.45960 (5)0.23525 (4)0.02443 (14)
C10.7721 (3)0.2712 (2)0.13281 (17)0.0232 (5)
C20.8616 (3)0.3495 (2)0.09128 (18)0.0266 (5)
C30.9860 (3)0.3337 (2)0.0074 (2)0.0332 (6)
H31.04540.3866−0.01780.043*
C41.0193 (3)0.2369 (2)−0.0377 (2)0.0344 (6)
H41.10210.2252−0.09430.045*
C50.9317 (3)0.1564 (2)−0.00032 (19)0.0302 (5)
H50.95420.0922−0.03190.039*
C60.8106 (3)0.1747 (2)0.08503 (17)0.0238 (5)
O10.72162 (19)0.09514 (15)0.12318 (13)0.0288 (4)
O20.8238 (2)0.44822 (15)0.13463 (13)0.0334 (4)
N10.4599 (2)0.07942 (19)0.21028 (15)0.0307 (5)
C70.4193 (3)0.1359 (3)0.1142 (2)0.0449 (8)
H7A0.50740.13940.05650.058*
H7B0.3640.21330.12180.058*
C80.3280 (4)0.0702 (5)0.0927 (3)0.0780 (14)
H8A0.3862−0.00540.08070.101*
H8B0.30.10850.03020.101*
C90.1899 (4)0.0598 (4)0.1828 (3)0.0644 (11)
H9A0.12530.13450.18970.084*
H9B0.13770.01150.16950.084*
C100.2330 (4)0.0087 (3)0.2823 (3)0.0585 (9)
H10A0.1450.00940.34060.076*
H10B0.2853−0.07010.27870.076*
C110.3273 (4)0.0728 (4)0.2992 (2)0.0551 (9)
H11A0.27140.14940.30990.072*
H11B0.35650.03570.36140.072*
N20.6376 (2)0.01734 (18)0.32605 (16)0.0306 (5)
C120.6752 (3)0.0430 (3)0.41152 (19)0.0321 (6)
H12A0.62470.00290.47680.042*
H12B0.64220.12420.41450.042*
C130.8394 (3)0.0077 (2)0.3971 (2)0.0340 (6)
H13A0.86050.02020.45690.044*
H13B0.88920.05440.33620.044*
C140.8968 (3)−0.1179 (3)0.3840 (2)0.0432 (7)
H14A1.0029−0.13730.36910.056*
H14B0.8563−0.16520.44810.056*
C150.8537 (4)−0.1412 (3)0.2961 (3)0.0448 (7)
H15A0.8843−0.22220.29210.058*
H15B0.904−0.10090.23080.058*
C160.6882 (3)−0.1029 (2)0.3126 (2)0.0424 (7)
H16A0.6644−0.11360.25330.055*
H16B0.6382−0.14930.37360.055*
N30.5935 (3)0.59172 (19)0.19468 (17)0.0358 (5)
C170.5694 (4)0.6169 (3)0.0915 (2)0.0574 (9)
H17A0.64090.56310.04820.075*
H17B0.58390.69290.05910.075*
C180.4161 (5)0.6095 (4)0.0985 (3)0.0741 (13)
H18A0.40580.53110.12270.096*
H18B0.40160.63180.02990.096*
C190.2992 (4)0.6858 (4)0.1717 (3)0.0727 (12)
H19A0.30110.76510.14330.095*
H19B0.20290.67460.17860.095*
C200.3262 (4)0.6582 (3)0.2774 (3)0.0606 (9)
H20A0.31030.58250.30990.079*
H20B0.25710.71240.32130.079*
C210.4819 (4)0.6631 (3)0.2676 (2)0.0458 (7)
H21A0.49240.74160.24480.06*
H21B0.49880.63870.33540.06*
N40.7223 (2)0.47366 (18)0.33326 (16)0.0297 (5)
C220.7178 (3)0.3868 (2)0.4260 (2)0.0388 (7)
H22A0.65790.33580.42750.05*
H22B0.67260.42350.48740.05*
C230.8690 (4)0.3190 (3)0.4275 (3)0.0586 (9)
H23A0.91210.27750.36890.076*
H23B0.86330.2640.49070.076*
C240.9645 (4)0.3990 (4)0.4220 (4)0.0800 (14)
H24A1.06370.35580.41890.104*
H24B0.92630.43470.48410.104*
C250.9672 (4)0.4908 (4)0.3267 (3)0.0702 (11)
H25A1.02220.54430.32750.091*
H25B1.01670.45570.26450.091*
C260.8136 (3)0.5542 (3)0.3239 (2)0.0428 (7)
H26A0.7690.59860.38050.056*
H26B0.81810.60650.25920.056*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd10.01969 (10)0.02554 (12)0.01935 (10)−0.00848 (8)−0.00401 (7)−0.00008 (7)
Br10.02724 (14)0.04573 (19)0.03679 (16)−0.01067 (13)0.00621 (11)−0.00854 (12)
P10.0256 (3)0.0282 (3)0.0210 (3)−0.0126 (3)−0.0072 (2)0.0025 (2)
P20.0274 (3)0.0246 (3)0.0212 (3)−0.0093 (3)−0.0055 (2)−0.0010 (2)
C10.0224 (11)0.0271 (13)0.0203 (11)−0.0068 (10)−0.0082 (9)0.0003 (9)
C20.0281 (12)0.0269 (13)0.0241 (12)−0.0088 (11)−0.0062 (10)−0.0008 (10)
C30.0313 (13)0.0365 (15)0.0299 (13)−0.0170 (12)−0.0014 (11)−0.0006 (11)
C40.0280 (13)0.0405 (16)0.0271 (13)−0.0089 (13)0.0012 (10)−0.0024 (11)
C50.0341 (13)0.0303 (14)0.0234 (12)−0.0066 (12)−0.0052 (10)−0.0039 (10)
C60.0251 (11)0.0252 (13)0.0201 (11)−0.0079 (10)−0.0077 (9)0.0032 (9)
O10.0328 (9)0.0291 (10)0.0252 (8)−0.0143 (8)−0.0041 (7)−0.0026 (7)
O20.0353 (10)0.0318 (10)0.0307 (9)−0.0190 (9)0.0050 (8)−0.0073 (7)
N10.0331 (11)0.0415 (13)0.0233 (10)−0.0206 (10)−0.0130 (9)0.0060 (9)
C70.0425 (16)0.066 (2)0.0253 (14)−0.0202 (15)−0.0163 (12)0.0139 (13)
C80.062 (2)0.148 (4)0.0414 (19)−0.045 (3)−0.0186 (17)−0.015 (2)
C90.0439 (18)0.113 (3)0.0499 (19)−0.034 (2)−0.0188 (15)−0.010 (2)
C100.0436 (17)0.080 (3)0.057 (2)−0.0337 (19)−0.0175 (16)0.0076 (18)
C110.0447 (17)0.100 (3)0.0267 (15)−0.0359 (19)−0.0106 (13)0.0033 (15)
N20.0343 (11)0.0334 (12)0.0278 (11)−0.0147 (10)−0.0152 (9)0.0068 (9)
C120.0277 (12)0.0469 (16)0.0203 (12)−0.0093 (12)−0.0078 (10)0.0002 (10)
C130.0291 (13)0.0451 (17)0.0317 (13)−0.0132 (13)−0.0128 (11)−0.0009 (11)
C140.0326 (14)0.0423 (18)0.0515 (18)−0.0083 (14)−0.0169 (13)0.0062 (14)
C150.0546 (18)0.0266 (15)0.0528 (18)−0.0091 (15)−0.0173 (15)−0.0020 (13)
C160.0568 (18)0.0317 (15)0.0480 (17)−0.0222 (15)−0.0279 (15)0.0106 (12)
N30.0479 (13)0.0310 (13)0.0253 (11)−0.0048 (11)−0.0132 (10)0.0012 (9)
C170.086 (3)0.052 (2)0.0294 (16)−0.0068 (19)−0.0281 (17)0.0096 (14)
C180.110 (3)0.064 (2)0.069 (3)−0.012 (3)−0.068 (3)0.004 (2)
C190.064 (2)0.064 (3)0.092 (3)−0.007 (2)−0.050 (2)0.017 (2)
C200.0463 (18)0.053 (2)0.066 (2)0.0032 (18)−0.0169 (17)0.0070 (18)
C210.0547 (18)0.0347 (17)0.0434 (17)0.0031 (15)−0.0182 (15)−0.0063 (13)
N40.0347 (11)0.0320 (12)0.0272 (10)−0.0135 (10)−0.0127 (9)−0.0001 (9)
C220.0485 (16)0.0446 (17)0.0303 (14)−0.0199 (14)−0.0188 (13)0.0043 (12)
C230.064 (2)0.047 (2)0.072 (2)−0.0073 (18)−0.044 (2)0.0058 (17)
C240.057 (2)0.092 (3)0.106 (3)−0.024 (2)−0.055 (2)0.013 (3)
C250.045 (2)0.095 (3)0.085 (3)−0.038 (2)−0.0196 (19)−0.013 (2)
C260.0592 (19)0.0417 (17)0.0395 (15)−0.0290 (16)−0.0175 (14)−0.0022 (12)
Geometric parameters (Å, °) top
Pd1—C11.988 (2)C13—H13A0.9700
Pd1—P12.2808 (7)C13—H13B0.9700
Pd1—P22.2891 (7)C14—C151.521 (4)
Pd1—Br12.5066 (7)C14—H14A0.9700
P1—N21.643 (2)C14—H14B0.9700
P1—O11.6549 (19)C15—C161.524 (4)
P1—N11.6762 (18)C15—H15A0.9700
P2—N41.631 (2)C15—H15B0.9700
P2—O21.6563 (19)C16—H16A0.9700
P2—N31.663 (2)C16—H16B0.9700
C1—C21.388 (3)N3—C211.464 (4)
C1—C61.395 (3)N3—C171.471 (3)
C2—O21.386 (3)C17—C181.514 (6)
C2—C31.386 (4)C17—H17A0.9700
C3—C41.384 (4)C17—H17B0.9700
C3—H30.9300C18—C191.519 (6)
C4—C51.397 (4)C18—H18A0.9700
C4—H40.9300C18—H18B0.9700
C5—C61.383 (4)C19—C201.516 (5)
C5—H50.9300C19—H19A0.9700
C6—O11.397 (3)C19—H19B0.9700
N1—C71.476 (3)C20—C211.517 (5)
N1—C111.478 (4)C20—H20A0.9700
C7—C81.502 (5)C20—H20B0.9700
C7—H7A0.9700C21—H21A0.9700
C7—H7B0.9700C21—H21B0.9700
C8—C91.526 (5)N4—C221.465 (3)
C8—H8A0.9700N4—C261.477 (3)
C8—H8B0.9700C22—C231.500 (4)
C9—C101.519 (5)C22—H22A0.9700
C9—H9A0.9700C22—H22B0.9700
C9—H9B0.9700C23—C241.520 (5)
C10—C111.479 (4)C23—H23A0.9700
C10—H10A0.9700C23—H23B0.9700
C10—H10B0.9700C24—C251.524 (6)
C11—H11A0.9700C24—H24A0.9700
C11—H11B0.9700C24—H24B0.9700
N2—C161.464 (4)C25—C261.511 (5)
N2—C121.470 (3)C25—H25A0.9700
C12—C131.515 (3)C25—H25B0.9700
C12—H12A0.9700C26—H26A0.9700
C12—H12B0.9700C26—H26B0.9700
C13—C141.527 (4)
C1—Pd1—P180.14 (7)H13A—C13—H13B108.1
C1—Pd1—P280.63 (7)C15—C14—C13110.3 (2)
P1—Pd1—P2160.31 (3)C15—C14—H14A109.6
C1—Pd1—Br1179.28 (7)C13—C14—H14A109.6
P1—Pd1—Br199.20 (3)C15—C14—H14B109.6
P2—Pd1—Br1100.00 (3)C13—C14—H14B109.6
N2—P1—O1108.07 (11)H14A—C14—H14B108.1
N2—P1—N1103.23 (10)C14—C15—C16111.1 (3)
O1—P1—N197.66 (10)C14—C15—H15A109.4
N2—P1—Pd1113.99 (8)C16—C15—H15A109.4
O1—P1—Pd1104.72 (6)C14—C15—H15B109.4
N1—P1—Pd1126.94 (9)C16—C15—H15B109.4
N4—P2—O2107.57 (10)H15A—C15—H15B108.0
N4—P2—N3103.59 (11)N2—C16—C15110.5 (2)
O2—P2—N397.15 (11)N2—C16—H16A109.5
N4—P2—Pd1115.52 (8)C15—C16—H16A109.5
O2—P2—Pd1103.76 (7)N2—C16—H16B109.5
N3—P2—Pd1126.50 (8)C15—C16—H16B109.5
C2—C1—C6117.1 (2)H16A—C16—H16B108.1
C2—C1—Pd1121.52 (19)C21—N3—C17112.6 (2)
C6—C1—Pd1121.40 (16)C21—N3—P2121.29 (18)
O2—C2—C3118.6 (2)C17—N3—P2118.4 (2)
O2—C2—C1118.6 (2)N3—C17—C18111.5 (3)
C3—C2—C1122.8 (2)N3—C17—H17A109.3
C4—C3—C2118.0 (2)C18—C17—H17A109.3
C4—C3—H3121.0N3—C17—H17B109.3
C2—C3—H3121.0C18—C17—H17B109.3
C3—C4—C5121.6 (2)H17A—C17—H17B108.0
C3—C4—H4119.2C17—C18—C19111.7 (3)
C5—C4—H4119.2C17—C18—H18A109.3
C6—C5—C4118.1 (2)C19—C18—H18A109.3
C6—C5—H5120.9C17—C18—H18B109.3
C4—C5—H5120.9C19—C18—H18B109.3
C5—C6—C1122.4 (2)H18A—C18—H18B107.9
C5—C6—O1118.8 (2)C20—C19—C18110.2 (3)
C1—C6—O1118.8 (2)C20—C19—H19A109.6
C6—O1—P1113.66 (15)C18—C19—H19A109.6
C2—O2—P2115.47 (14)C20—C19—H19B109.6
C7—N1—C11110.7 (2)C18—C19—H19B109.6
C7—N1—P1117.55 (17)H19A—C19—H19B108.1
C11—N1—P1115.22 (17)C19—C20—C21110.7 (3)
N1—C7—C8109.6 (3)C19—C20—H20A109.5
N1—C7—H7A109.8C21—C20—H20A109.5
C8—C7—H7A109.8C19—C20—H20B109.5
N1—C7—H7B109.8C21—C20—H20B109.5
C8—C7—H7B109.8H20A—C20—H20B108.1
H7A—C7—H7B108.2N3—C21—C20113.2 (3)
C7—C8—C9111.6 (3)N3—C21—H21A108.9
C7—C8—H8A109.3C20—C21—H21A108.9
C9—C8—H8A109.3N3—C21—H21B108.9
C7—C8—H8B109.3C20—C21—H21B108.9
C9—C8—H8B109.3H21A—C21—H21B107.8
H8A—C8—H8B108.0C22—N4—C26112.93 (19)
C10—C9—C8109.3 (3)C22—N4—P2122.37 (16)
C10—C9—H9A109.8C26—N4—P2122.27 (17)
C8—C9—H9A109.8N4—C22—C23111.4 (3)
C10—C9—H9B109.8N4—C22—H22A109.3
C8—C9—H9B109.8C23—C22—H22A109.3
H9A—C9—H9B108.3N4—C22—H22B109.3
C11—C10—C9111.5 (3)C23—C22—H22B109.3
C11—C10—H10A109.3H22A—C22—H22B108.0
C9—C10—H10A109.3C22—C23—C24109.5 (3)
C11—C10—H10B109.3C22—C23—H23A109.8
C9—C10—H10B109.3C24—C23—H23A109.8
H10A—C10—H10B108.0C22—C23—H23B109.8
N1—C11—C10111.8 (3)C24—C23—H23B109.8
N1—C11—H11A109.3H23A—C23—H23B108.2
C10—C11—H11A109.3C23—C24—C25110.7 (3)
N1—C11—H11B109.3C23—C24—H24A109.5
C10—C11—H11B109.3C25—C24—H24A109.5
H11A—C11—H11B107.9C23—C24—H24B109.5
C16—N2—C12113.5 (2)C25—C24—H24B109.5
C16—N2—P1122.31 (18)H24A—C24—H24B108.1
C12—N2—P1121.26 (18)C26—C25—C24111.3 (3)
N2—C12—C13111.1 (2)C26—C25—H25A109.4
N2—C12—H12A109.4C24—C25—H25A109.4
C13—C12—H12A109.4C26—C25—H25B109.4
N2—C12—H12B109.4C24—C25—H25B109.4
C13—C12—H12B109.4H25A—C25—H25B108.0
H12A—C12—H12B108.0N4—C26—C25110.7 (3)
C12—C13—C14110.7 (2)N4—C26—H26A109.5
C12—C13—H13A109.5C25—C26—H26A109.5
C14—C13—H13A109.5N4—C26—H26B109.5
C12—C13—H13B109.5C25—C26—H26B109.5
C14—C13—H13B109.5H26A—C26—H26B108.1
C1—Pd1—P1—N2109.12 (11)Pd1—P1—N1—C11−73.1 (2)
P2—Pd1—P1—N296.51 (11)C11—N1—C7—C8−59.2 (4)
Br1—Pd1—P1—N2−70.58 (9)P1—N1—C7—C8165.5 (3)
C1—Pd1—P1—O1−8.77 (9)N1—C7—C8—C957.9 (4)
P2—Pd1—P1—O1−21.39 (10)C7—C8—C9—C10−54.5 (5)
Br1—Pd1—P1—O1171.52 (6)C8—C9—C10—C1153.1 (5)
C1—Pd1—P1—N1−120.48 (11)C7—N1—C11—C1059.2 (4)
P2—Pd1—P1—N1−133.10 (10)P1—N1—C11—C10−164.4 (2)
Br1—Pd1—P1—N159.81 (9)C9—C10—C11—N1−56.2 (4)
C1—Pd1—P2—N4−117.13 (11)O1—P1—N2—C16−44.3 (2)
P1—Pd1—P2—N4−104.54 (11)N1—P1—N2—C1658.5 (2)
Br1—Pd1—P2—N462.52 (10)Pd1—P1—N2—C16−160.24 (17)
C1—Pd1—P2—O20.34 (9)O1—P1—N2—C12115.2 (2)
P1—Pd1—P2—O212.94 (10)N1—P1—N2—C12−142.08 (19)
Br1—Pd1—P2—O2180.00 (7)Pd1—P1—N2—C12−0.8 (2)
C1—Pd1—P2—N3110.24 (12)C16—N2—C12—C1356.8 (3)
P1—Pd1—P2—N3122.84 (12)P1—N2—C12—C13−104.4 (2)
Br1—Pd1—P2—N3−70.10 (11)N2—C12—C13—C14−54.9 (3)
P1—Pd1—C1—C2−175.34 (19)C12—C13—C14—C1554.5 (3)
P2—Pd1—C1—C20.39 (17)C13—C14—C15—C16−54.8 (3)
P1—Pd1—C1—C65.65 (16)C12—N2—C16—C15−56.5 (3)
P2—Pd1—C1—C6−178.63 (18)P1—N2—C16—C15104.4 (2)
C6—C1—C2—O2177.85 (19)C14—C15—C16—N255.2 (3)
Pd1—C1—C2—O2−1.2 (3)N4—P2—N3—C21−47.9 (2)
C6—C1—C2—C3−1.3 (3)O2—P2—N3—C21−158.0 (2)
Pd1—C1—C2—C3179.68 (18)Pd1—P2—N3—C2189.0 (2)
O2—C2—C3—C4−177.5 (2)N4—P2—N3—C17164.8 (2)
C1—C2—C3—C41.6 (4)O2—P2—N3—C1754.7 (2)
C2—C3—C4—C5−0.4 (4)Pd1—P2—N3—C17−58.3 (3)
C3—C4—C5—C6−1.0 (4)C21—N3—C17—C18−54.1 (4)
C4—C5—C6—C11.4 (3)P2—N3—C17—C1895.9 (3)
C4—C5—C6—O1179.8 (2)N3—C17—C18—C1954.9 (4)
C2—C1—C6—C5−0.3 (3)C17—C18—C19—C20−54.8 (4)
Pd1—C1—C6—C5178.77 (17)C18—C19—C20—C2153.4 (4)
C2—C1—C6—O1−178.70 (19)C17—N3—C21—C2054.1 (3)
Pd1—C1—C6—O10.4 (3)P2—N3—C21—C20−94.9 (3)
C5—C6—O1—P1172.54 (17)C19—C20—C21—N3−53.7 (4)
C1—C6—O1—P1−9.0 (2)O2—P2—N4—C22−113.9 (2)
N2—P1—O1—C6−110.08 (16)N3—P2—N4—C22143.9 (2)
N1—P1—O1—C6143.25 (16)Pd1—P2—N4—C221.4 (3)
Pd1—P1—O1—C611.78 (15)O2—P2—N4—C2647.1 (2)
C3—C2—O2—P2−179.37 (18)N3—P2—N4—C26−55.1 (2)
C1—C2—O2—P21.5 (3)Pd1—P2—N4—C26162.4 (2)
N4—P2—O2—C2121.83 (17)C26—N4—C22—C23−58.1 (3)
N3—P2—O2—C2−131.42 (17)P2—N4—C22—C23104.5 (3)
Pd1—P2—O2—C2−1.04 (17)N4—C22—C23—C2457.4 (4)
N2—P1—N1—C7−165.4 (2)C22—C23—C24—C25−55.9 (5)
O1—P1—N1—C7−54.8 (2)C23—C24—C25—C2654.6 (5)
Pd1—P1—N1—C760.2 (2)C22—N4—C26—C2555.4 (3)
N2—P1—N1—C1161.2 (2)P2—N4—C26—C25−107.3 (3)
O1—P1—N1—C11171.9 (2)C24—C25—C26—N4−53.4 (4)
Selected geometric parameters (Å, °) top
Pd1—C11.988 (2)P1—N11.6762 (18)
Pd1—P12.2808 (7)P2—N41.631 (2)
Pd1—P22.2891 (7)P2—O21.6563 (19)
Pd1—Br12.5066 (7)P2—N31.663 (2)
P1—N21.643 (2)C2—O21.386 (3)
P1—O11.6549 (19)C6—O11.397 (3)
C1—Pd1—P180.14 (7)P1—Pd1—Br199.20 (3)
C1—Pd1—P280.63 (7)P2—Pd1—Br1100.00 (3)
P1—Pd1—P2160.31 (3)O1—P1—Pd1104.72 (6)
C1—Pd1—Br1179.28 (7)O2—P2—Pd1103.76 (7)
Acknowledgements top

The authors thank the University of Zürich and the Swiss National Science Foundation for financial support.

references
References top

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