Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010302170X/tr1065sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010302170X/tr1065Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010302170X/tr1065IIsup3.hkl |
CCDC references: 226113; 226114
An NPN ligand with a dihydrooxazole moiety was prepared according to the method for preparing the NPN ligand with a phenethylamine moiety (Yamada et al., 1996), except for the use of (S)-4-tert-butyl-2-phenyl-2,3-dihydrooxazole (Bernardinelli et al., 2001) instead of (S)—N,N-dimethyl-1-phenylethylamine. For the preparation of (I), the ligand was stirred with an equimolar amount of [Pd(µ-Cl)(η3-allyl)]2 in chloroform overnight at room temperature. A methanol solution of NH4PF6 was added and the mixture was stirred for 2.5 h, before being washed with water and then evaporated. The residue was purified by reprecipitation from chloroform/ether, and recrystallization from chloroform/hexane gave the π-allyl derivative of (I) in the form of a white solid. This white solid was mixed with 3-penten-2-yl acetate (5 equivalents) and dimethyl sodiomalonate (3 equivalents) in tetrahydrofuran at 298 K for 48 h, before addition of a NH4PF6 solution in methanol. The reaction mixture was evaporated, extracted with dichloromethane and evaporated again. The residual oil was purified by reprecipitation from dichloromethane/ether, and recrystallization from dichloromethane/ether gave pale yellow crystals in an 87% yield. Single crystals suitable for X-ray diffraction analysis were obtained by recrystallization from dichloromethane/ether. The 1H NMR spectrum shows strong resonances due to a main species with weak resonances, which are in turn? due to the presence of a small amount of a minor species. 1H NMR (CDCl3, 400 MHz): δ 0.44 (9H, s, Me), 0.57 (9H, s, Me), 0.88 (3H, dd, Me on π-allyl), 1.87 (3H, dd, Me on π-allyl), 2.74 (1H, dq, allylic H), 3.79–4.62 (6H, m, methyne and methylene), 4.52 (1H, m, allylic H), 5.30 (1H, dd, allylic H), 6.87–8.30 (13H, m, Ph). For the prepartaion of (II), the ligand was stirred with an equimolar amount of [PdCl2(PhCN)2] in benzene overnight. The precipitate was collected and recrystallized from dichloromethane/hexane to give orange crystals (87% yield). Single crystals suitable for X-ray diffraction were obtained by recrystallization from the same solvents. 1H NMR (CDCl3, 400 MHz): δ 0.56 (9H, s, Me), 0.76 (9H, s, Me), 4.06 (1H, t, methylene), 4.39 (1H, t, methyne), 4.49 (1H, t, methylene), 4.53 (1H, dd, methylene), 4.96 (1H, t, methylene), 5.55 (1H, m, methylene), 6.88 (1H, dd, Ph), 7.00 (1H, dd, Ph), 7.36–7.62 (9H, m, Ph), 8.06 (1H, dd, Ph), 8.19 (1H, dd, Ph).
For both compounds, all H atoms bonded to C atoms, except for atoms H9A and H22A of (II), were included in calculated positions, with C—H distances of 0.93 Å for aromatic and allylic H atoms, 0.98 Å for methyne atoms, 0.97 Å for methylene atoms, and 0.96 Å for methyl atoms. Atoms H9A and H22A of (II) were placed in positions determined from a difference Fourier map, and constrained to ride on the coordinates of their parent atoms. In (I), there are two large and two smaller voids (in total ca 110.6 Å3) per unit cell, the larger probably hosting a disordered solvent molecule. A residual peak of 1.2 e Å−3 was localized in this void, but it could not be verified what this peak represented through refinement. A disordered solvent correction based on the SQUEEZE algorithm (van der Sluis & Spek, 1990) in PLATON (Spek, 2003) afforded solvent-free reflection data and estimated that a total of 12 electrons were unaccounted for. Refinement with the solvent-free data improves the minimum residual electron density from −0.304 to −0.275 e Å−3, the maximum residual electron density from 1.181 to 0.575 e Å−3, and wR from 0.0936 to 0.0743.
For both compounds, data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997). Software used to prepare material for publication: SHELXTL (Bruker, 1997) and PLATON (Spek, 2003) for (I); SHELXTL for (II).
Fig. 1. ORTEP-3 (Farrugia, 1997) diagram of (I), showing 50% probability displacement ellipsoids. | |
Fig. 2. ORTEP-3 (Farrugia, 1997) diagram of (II), showing 50% probabilty displacement ellipsoids. |
[Pd(C32H37N2O2P)(C5H9)]PF6 | F(000) = 856 |
Mr = 833.10 | Dx = 1.436 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 972 reflections |
a = 10.3152 (13) Å | θ = 2.0–27.8° |
b = 13.5764 (17) Å | µ = 0.63 mm−1 |
c = 13.8415 (18) Å | T = 293 K |
β = 96.345 (2)° | Block, pale yellow |
V = 1926.5 (4) Å3 | 0.8 × 0.4 × 0.4 mm |
Z = 2 |
Bruker SMART APEX CCD diffractometer | 8317 independent reflections |
Radiation source: fine-focus sealed tube | 7836 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.014 |
Detector resolution: 66 pixels mm-1 | θmax = 27.8°, θmin = 2.0° |
ω scans | h = −13→10 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −17→17 |
Tmin = 0.536, Tmax = 0.634 | l = −17→14 |
12103 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.030 | H-atom parameters constrained |
wR(F2) = 0.074 | w = 1/[σ2(Fo2) + (0.0492P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max = 0.001 |
8317 reflections | Δρmax = 0.58 e Å−3 |
459 parameters | Δρmin = −0.28 e Å−3 |
1 restraint | Absolute structure: Flack (1983), 3757 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.001 (17) |
[Pd(C32H37N2O2P)(C5H9)]PF6 | V = 1926.5 (4) Å3 |
Mr = 833.10 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 10.3152 (13) Å | µ = 0.63 mm−1 |
b = 13.5764 (17) Å | T = 293 K |
c = 13.8415 (18) Å | 0.8 × 0.4 × 0.4 mm |
β = 96.345 (2)° |
Bruker SMART APEX CCD diffractometer | 8317 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 7836 reflections with I > 2σ(I) |
Tmin = 0.536, Tmax = 0.634 | Rint = 0.014 |
12103 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | H-atom parameters constrained |
wR(F2) = 0.074 | Δρmax = 0.58 e Å−3 |
S = 1.00 | Δρmin = −0.28 e Å−3 |
8317 reflections | Absolute structure: Flack (1983), 3757 Friedel pairs |
459 parameters | Absolute structure parameter: 0.001 (17) |
1 restraint |
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. |
x | y | z | Uiso*/Ueq | ||
Pd1 | 0.921373 (16) | 0.473424 (15) | 0.821573 (11) | 0.03385 (6) | |
P1 | 0.97012 (6) | 0.40147 (5) | 0.68067 (5) | 0.03107 (13) | |
N1 | 0.8113 (2) | 0.57856 (16) | 0.73314 (16) | 0.0368 (5) | |
N2 | 0.7852 (3) | 0.2731 (2) | 0.7696 (2) | 0.0429 (6) | |
O1 | 0.6706 (2) | 0.64276 (17) | 0.61573 (17) | 0.0592 (6) | |
O2 | 0.8575 (3) | 0.1391 (2) | 0.8539 (2) | 0.0700 (8) | |
C1 | 0.8266 (2) | 0.4037 (2) | 0.58980 (18) | 0.0335 (5) | |
C2 | 0.8104 (3) | 0.3296 (2) | 0.5204 (2) | 0.0445 (6) | |
H2A | 0.8697 | 0.2778 | 0.5231 | 0.053* | |
C3 | 0.7071 (4) | 0.3313 (2) | 0.4468 (2) | 0.0535 (8) | |
H3A | 0.6986 | 0.2815 | 0.4004 | 0.064* | |
C4 | 0.6186 (3) | 0.4059 (3) | 0.4427 (2) | 0.0532 (8) | |
H4A | 0.5496 | 0.4074 | 0.3934 | 0.064* | |
C5 | 0.6315 (2) | 0.4786 (3) | 0.51117 (19) | 0.0456 (6) | |
H5A | 0.5691 | 0.5283 | 0.5087 | 0.055* | |
C6 | 0.7359 (2) | 0.4805 (3) | 0.58514 (16) | 0.0347 (5) | |
C7 | 0.7436 (3) | 0.5665 (2) | 0.6504 (2) | 0.0387 (6) | |
C8 | 0.6779 (4) | 0.7150 (3) | 0.6931 (3) | 0.0721 (11) | |
H8A | 0.5992 | 0.7139 | 0.7257 | 0.086* | |
H8B | 0.6897 | 0.7807 | 0.6680 | 0.086* | |
C9 | 0.7952 (4) | 0.6841 (2) | 0.7619 (3) | 0.0482 (9) | |
H9A | 0.7718 | 0.6861 | 0.8286 | 0.058* | |
C10 | 0.9202 (5) | 0.7451 (2) | 0.7569 (3) | 0.0603 (10) | |
C11 | 1.0309 (4) | 0.7077 (3) | 0.8293 (4) | 0.0787 (12) | |
H11A | 1.0517 | 0.6412 | 0.8134 | 0.118* | |
H11B | 1.0046 | 0.7097 | 0.8937 | 0.118* | |
H11C | 1.1063 | 0.7486 | 0.8266 | 0.118* | |
C12 | 0.9623 (6) | 0.7449 (3) | 0.6533 (3) | 0.0891 (15) | |
H12A | 1.0353 | 0.7883 | 0.6508 | 0.134* | |
H12B | 0.8911 | 0.7668 | 0.6079 | 0.134* | |
H12C | 0.9868 | 0.6793 | 0.6366 | 0.134* | |
C13 | 0.8870 (6) | 0.8527 (3) | 0.7854 (4) | 0.0911 (15) | |
H13A | 0.8501 | 0.8522 | 0.8461 | 0.137* | |
H13B | 0.8254 | 0.8805 | 0.7358 | 0.137* | |
H13C | 0.9652 | 0.8916 | 0.7919 | 0.137* | |
C14 | 1.0319 (3) | 0.2750 (2) | 0.67755 (19) | 0.0350 (5) | |
C15 | 1.1345 (3) | 0.2545 (2) | 0.6220 (2) | 0.0421 (6) | |
H15A | 1.1661 | 0.3044 | 0.5849 | 0.051* | |
C16 | 1.1899 (3) | 0.1614 (3) | 0.6212 (3) | 0.0519 (8) | |
H16A | 1.2546 | 0.1484 | 0.5811 | 0.062* | |
C17 | 1.1495 (3) | 0.0887 (2) | 0.6791 (3) | 0.0576 (9) | |
H17A | 1.1896 | 0.0273 | 0.6810 | 0.069* | |
C18 | 1.0492 (3) | 0.1065 (2) | 0.7348 (3) | 0.0527 (8) | |
H18A | 1.0224 | 0.0568 | 0.7743 | 0.063* | |
C19 | 0.9869 (3) | 0.1989 (2) | 0.7327 (2) | 0.0381 (6) | |
C20 | 0.8716 (3) | 0.2090 (2) | 0.7844 (2) | 0.0431 (7) | |
C21 | 0.7362 (4) | 0.1635 (4) | 0.8922 (4) | 0.0812 (13) | |
H21A | 0.7519 | 0.1804 | 0.9606 | 0.097* | |
H21B | 0.6759 | 0.1085 | 0.8847 | 0.097* | |
C22 | 0.6823 (3) | 0.2512 (3) | 0.8328 (2) | 0.0472 (7) | |
H22A | 0.6759 | 0.3070 | 0.8769 | 0.057* | |
C23 | 0.5493 (3) | 0.2365 (3) | 0.7739 (2) | 0.0527 (8) | |
C24 | 0.5082 (5) | 0.3299 (5) | 0.7211 (5) | 0.1038 (19) | |
H24A | 0.5072 | 0.3829 | 0.7670 | 0.156* | |
H24B | 0.4226 | 0.3217 | 0.6872 | 0.156* | |
H24C | 0.5688 | 0.3450 | 0.6753 | 0.156* | |
C25 | 0.4477 (4) | 0.2099 (4) | 0.8415 (3) | 0.0696 (11) | |
H25A | 0.4439 | 0.2609 | 0.8891 | 0.104* | |
H25B | 0.4712 | 0.1488 | 0.8736 | 0.104* | |
H25C | 0.3639 | 0.2032 | 0.8043 | 0.104* | |
C26 | 0.5597 (5) | 0.1534 (5) | 0.6989 (4) | 0.0978 (18) | |
H26A | 0.4744 | 0.1383 | 0.6674 | 0.147* | |
H26B | 0.5964 | 0.0957 | 0.7315 | 0.147* | |
H26C | 0.6147 | 0.1745 | 0.6513 | 0.147* | |
C27 | 1.0906 (2) | 0.4714 (3) | 0.62126 (17) | 0.0370 (4) | |
C28 | 1.0786 (3) | 0.4918 (3) | 0.5229 (2) | 0.0510 (8) | |
H28A | 1.0049 | 0.4710 | 0.4833 | 0.061* | |
C29 | 1.1767 (4) | 0.5433 (3) | 0.4825 (3) | 0.0653 (10) | |
H29A | 1.1681 | 0.5572 | 0.4163 | 0.078* | |
C30 | 1.2860 (4) | 0.5736 (3) | 0.5409 (3) | 0.0654 (10) | |
H30A | 1.3515 | 0.6077 | 0.5141 | 0.079* | |
C31 | 1.2986 (3) | 0.5536 (3) | 0.6386 (3) | 0.0629 (9) | |
H31A | 1.3732 | 0.5735 | 0.6776 | 0.075* | |
C32 | 1.2002 (3) | 0.5035 (2) | 0.6795 (2) | 0.0487 (7) | |
H32A | 1.2082 | 0.4917 | 0.7461 | 0.058* | |
C33 | 0.7968 (5) | 0.5826 (4) | 1.0092 (3) | 0.0837 (13) | |
H33A | 0.7695 | 0.5668 | 1.0715 | 0.126* | |
H33B | 0.7220 | 0.5995 | 0.9648 | 0.126* | |
H33C | 0.8560 | 0.6374 | 1.0159 | 0.126* | |
C34 | 0.8612 (4) | 0.4988 (3) | 0.9726 (2) | 0.0718 (13) | |
H34A | 0.8027 | 0.4562 | 0.9379 | 0.086* | |
C35 | 0.9811 (4) | 0.4675 (4) | 0.9757 (2) | 0.0631 (9) | |
H35A | 1.0432 | 0.5047 | 1.0136 | 0.076* | |
C36 | 1.0282 (4) | 0.3867 (3) | 0.9302 (2) | 0.0562 (8) | |
H36A | 0.9668 | 0.3437 | 0.8992 | 0.067* | |
C37 | 1.1665 (5) | 0.3621 (4) | 0.9263 (3) | 0.0862 (14) | |
H37A | 1.2161 | 0.4216 | 0.9235 | 0.129* | |
H37B | 1.1751 | 0.3231 | 0.8694 | 0.129* | |
H37C | 1.1984 | 0.3254 | 0.9833 | 0.129* | |
P2 | 0.44253 (11) | 0.85731 (8) | 0.86591 (7) | 0.0659 (3) | |
F1 | 0.5563 (3) | 0.7860 (3) | 0.9042 (2) | 0.1181 (11) | |
F2 | 0.3303 (5) | 0.9273 (4) | 0.8246 (3) | 0.170 (2) | |
F3 | 0.3517 (4) | 0.8114 (4) | 0.9332 (3) | 0.1529 (17) | |
F4 | 0.3977 (3) | 0.7813 (3) | 0.7833 (2) | 0.1081 (10) | |
F5 | 0.5362 (5) | 0.9007 (4) | 0.7938 (3) | 0.1480 (15) | |
F6 | 0.4866 (5) | 0.9317 (3) | 0.9484 (3) | 0.1677 (19) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.03943 (9) | 0.03493 (9) | 0.02702 (8) | 0.00098 (10) | 0.00289 (6) | −0.00121 (10) |
P1 | 0.0323 (3) | 0.0318 (3) | 0.0289 (3) | 0.0022 (2) | 0.0027 (2) | −0.0004 (2) |
N1 | 0.0430 (12) | 0.0323 (11) | 0.0354 (12) | 0.0025 (9) | 0.0054 (9) | −0.0017 (9) |
N2 | 0.0381 (14) | 0.0435 (15) | 0.0474 (16) | −0.0035 (11) | 0.0059 (11) | 0.0058 (12) |
O1 | 0.0712 (15) | 0.0504 (13) | 0.0520 (13) | 0.0285 (11) | −0.0107 (11) | −0.0069 (10) |
O2 | 0.0646 (15) | 0.0747 (18) | 0.0732 (17) | 0.0079 (13) | 0.0186 (13) | 0.0375 (14) |
C1 | 0.0346 (12) | 0.0367 (12) | 0.0288 (12) | −0.0008 (10) | 0.0012 (9) | 0.0008 (10) |
C2 | 0.0501 (17) | 0.0423 (15) | 0.0395 (15) | 0.0031 (13) | −0.0021 (12) | −0.0048 (12) |
C3 | 0.068 (2) | 0.0479 (17) | 0.0419 (17) | −0.0042 (15) | −0.0073 (14) | −0.0114 (14) |
C4 | 0.0524 (17) | 0.0592 (19) | 0.0438 (16) | −0.0037 (15) | −0.0130 (13) | 0.0019 (15) |
C5 | 0.0366 (11) | 0.0532 (15) | 0.0452 (13) | 0.0026 (17) | −0.0037 (9) | 0.0041 (19) |
C6 | 0.0356 (11) | 0.0368 (13) | 0.0319 (10) | 0.0022 (14) | 0.0047 (8) | 0.0051 (14) |
C7 | 0.0403 (14) | 0.0373 (14) | 0.0391 (14) | 0.0083 (11) | 0.0075 (11) | 0.0009 (11) |
C8 | 0.096 (3) | 0.0522 (19) | 0.065 (2) | 0.033 (2) | −0.002 (2) | −0.0139 (17) |
C9 | 0.068 (2) | 0.0373 (18) | 0.0409 (18) | 0.0085 (15) | 0.0122 (16) | −0.0059 (14) |
C10 | 0.099 (3) | 0.0358 (16) | 0.048 (2) | −0.0079 (18) | 0.020 (2) | −0.0032 (14) |
C11 | 0.080 (3) | 0.067 (2) | 0.089 (3) | −0.028 (2) | 0.007 (2) | −0.007 (2) |
C12 | 0.137 (4) | 0.070 (3) | 0.068 (3) | −0.025 (3) | 0.046 (3) | 0.001 (2) |
C13 | 0.155 (5) | 0.0394 (19) | 0.080 (3) | −0.009 (2) | 0.017 (3) | −0.013 (2) |
C14 | 0.0350 (13) | 0.0338 (13) | 0.0349 (13) | 0.0048 (10) | −0.0018 (10) | −0.0032 (10) |
C15 | 0.0392 (14) | 0.0443 (15) | 0.0429 (15) | 0.0033 (12) | 0.0051 (11) | −0.0068 (12) |
C16 | 0.0465 (16) | 0.0522 (17) | 0.0560 (19) | 0.0137 (14) | 0.0006 (14) | −0.0150 (15) |
C17 | 0.0528 (19) | 0.0403 (16) | 0.076 (2) | 0.0155 (14) | −0.0074 (16) | −0.0136 (16) |
C18 | 0.0562 (18) | 0.0332 (14) | 0.066 (2) | 0.0032 (13) | −0.0063 (15) | 0.0020 (14) |
C19 | 0.0387 (14) | 0.0349 (13) | 0.0391 (15) | 0.0003 (11) | −0.0031 (11) | 0.0007 (11) |
C20 | 0.0452 (16) | 0.0409 (16) | 0.0418 (16) | −0.0083 (13) | −0.0021 (13) | 0.0063 (13) |
C21 | 0.056 (2) | 0.108 (3) | 0.081 (3) | 0.001 (2) | 0.016 (2) | 0.047 (3) |
C22 | 0.0439 (16) | 0.0573 (18) | 0.0416 (16) | −0.0083 (13) | 0.0095 (12) | −0.0008 (13) |
C23 | 0.0429 (16) | 0.070 (2) | 0.0467 (17) | −0.0061 (15) | 0.0099 (13) | −0.0011 (15) |
C24 | 0.058 (3) | 0.118 (4) | 0.136 (5) | 0.012 (3) | 0.015 (3) | 0.055 (4) |
C25 | 0.0475 (19) | 0.092 (3) | 0.071 (3) | −0.0161 (19) | 0.0179 (17) | −0.008 (2) |
C26 | 0.072 (3) | 0.133 (5) | 0.089 (3) | −0.020 (3) | 0.011 (2) | −0.053 (3) |
C27 | 0.0368 (11) | 0.0331 (10) | 0.0419 (12) | 0.0031 (16) | 0.0084 (9) | 0.0003 (17) |
C28 | 0.0496 (15) | 0.059 (2) | 0.0450 (15) | 0.0027 (14) | 0.0080 (12) | 0.0126 (14) |
C29 | 0.068 (2) | 0.076 (2) | 0.055 (2) | 0.0091 (19) | 0.0222 (17) | 0.0258 (19) |
C30 | 0.055 (2) | 0.058 (2) | 0.087 (3) | 0.0011 (16) | 0.0249 (19) | 0.025 (2) |
C31 | 0.0446 (17) | 0.064 (2) | 0.080 (3) | −0.0127 (16) | 0.0053 (16) | 0.0085 (19) |
C32 | 0.0435 (15) | 0.0546 (19) | 0.0480 (16) | −0.0047 (12) | 0.0051 (12) | 0.0083 (12) |
C33 | 0.106 (3) | 0.090 (3) | 0.062 (2) | 0.022 (3) | 0.036 (2) | 0.001 (2) |
C34 | 0.091 (3) | 0.095 (4) | 0.0286 (14) | 0.018 (2) | 0.0065 (15) | −0.0029 (16) |
C35 | 0.084 (2) | 0.072 (2) | 0.0308 (12) | 0.036 (2) | −0.0021 (13) | 0.005 (2) |
C36 | 0.070 (2) | 0.0575 (19) | 0.0378 (16) | 0.0049 (16) | −0.0094 (14) | 0.0055 (14) |
C37 | 0.081 (3) | 0.108 (4) | 0.065 (3) | 0.031 (3) | −0.012 (2) | 0.006 (2) |
P2 | 0.0817 (7) | 0.0694 (6) | 0.0465 (5) | 0.0103 (5) | 0.0066 (4) | −0.0005 (4) |
F1 | 0.117 (2) | 0.135 (3) | 0.095 (2) | 0.045 (2) | −0.0220 (17) | −0.008 (2) |
F2 | 0.209 (4) | 0.173 (4) | 0.121 (3) | 0.126 (4) | −0.011 (3) | 0.003 (3) |
F3 | 0.150 (3) | 0.224 (5) | 0.093 (2) | −0.021 (3) | 0.051 (2) | 0.022 (3) |
F4 | 0.112 (2) | 0.129 (3) | 0.0804 (18) | 0.003 (2) | −0.0045 (16) | −0.0332 (19) |
F5 | 0.181 (4) | 0.146 (3) | 0.124 (3) | −0.033 (3) | 0.050 (3) | 0.013 (3) |
F6 | 0.200 (4) | 0.156 (4) | 0.137 (3) | 0.019 (3) | −0.024 (3) | −0.086 (3) |
Pd1—C34 | 2.271 (3) | C17—H17A | 0.9300 |
Pd1—C35 | 2.155 (3) | C18—C19 | 1.408 (4) |
Pd1—C36 | 2.120 (3) | C18—H18A | 0.9300 |
Pd1—N1 | 2.125 (2) | C19—C20 | 1.461 (4) |
Pd1—P1 | 2.2864 (7) | C21—C22 | 1.517 (5) |
P1—C27 | 1.830 (3) | C21—H21A | 0.9700 |
P1—C14 | 1.833 (3) | C21—H21B | 0.9700 |
P1—C1 | 1.834 (3) | C22—C23 | 1.530 (4) |
N1—C7 | 1.284 (4) | C22—H22A | 0.9800 |
N1—C9 | 1.502 (4) | C23—C24 | 1.502 (6) |
N2—C20 | 1.246 (4) | C23—C25 | 1.523 (4) |
N2—C22 | 1.478 (4) | C23—C26 | 1.545 (6) |
O1—C7 | 1.338 (3) | C24—H24A | 0.9600 |
O1—C8 | 1.448 (4) | C24—H24B | 0.9600 |
O2—C20 | 1.371 (4) | C24—H24C | 0.9600 |
O2—C21 | 1.450 (5) | C25—H25A | 0.9600 |
C1—C2 | 1.389 (4) | C25—H25B | 0.9600 |
C1—C6 | 1.398 (4) | C25—H25C | 0.9600 |
C2—C3 | 1.390 (4) | C26—H26A | 0.9600 |
C2—H2A | 0.9300 | C26—H26B | 0.9600 |
C3—C4 | 1.361 (5) | C26—H26C | 0.9600 |
C3—H3A | 0.9300 | C27—C28 | 1.382 (4) |
C4—C5 | 1.365 (5) | C27—C32 | 1.384 (4) |
C4—H4A | 0.9300 | C28—C29 | 1.397 (5) |
C5—C6 | 1.402 (3) | C28—H28A | 0.9300 |
C5—H5A | 0.9300 | C29—C30 | 1.376 (6) |
C6—C7 | 1.473 (4) | C29—H29A | 0.9300 |
C8—C9 | 1.514 (5) | C30—C31 | 1.371 (6) |
C8—H8A | 0.9700 | C30—H30A | 0.9300 |
C8—H8B | 0.9700 | C31—C32 | 1.393 (4) |
C9—C10 | 1.540 (6) | C31—H31A | 0.9300 |
C9—H9A | 0.9800 | C32—H32A | 0.9300 |
C10—C11 | 1.521 (7) | C33—C34 | 1.438 (6) |
C10—C12 | 1.544 (5) | C33—H33A | 0.9600 |
C10—C13 | 1.561 (5) | C33—H33B | 0.9600 |
C11—H11A | 0.9600 | C33—H33C | 0.9600 |
C11—H11B | 0.9600 | C34—C35 | 1.304 (5) |
C11—H11C | 0.9600 | C34—H34A | 0.9300 |
C12—H12A | 0.9600 | C35—C36 | 1.380 (5) |
C12—H12B | 0.9600 | C35—H35A | 0.9300 |
C12—H12C | 0.9600 | C36—C37 | 1.472 (6) |
C13—H13A | 0.9600 | C36—H36A | 0.9300 |
C13—H13B | 0.9600 | C37—H37A | 0.9600 |
C13—H13C | 0.9600 | C37—H37B | 0.9600 |
C14—C19 | 1.395 (4) | C37—H37C | 0.9600 |
C14—C15 | 1.404 (4) | P2—F3 | 1.526 (4) |
C15—C16 | 1.389 (4) | P2—F6 | 1.555 (4) |
C15—H15A | 0.9300 | P2—F2 | 1.557 (4) |
C16—C17 | 1.365 (5) | P2—F1 | 1.568 (3) |
C16—H16A | 0.9300 | P2—F4 | 1.572 (3) |
C17—C18 | 1.378 (5) | P2—F5 | 1.578 (4) |
Pd1···N2 | 3.108 (3) | ||
C34—Pd1—P1 | 163.33 (12) | O2—C21—C22 | 105.1 (3) |
C35—Pd1—P1 | 139.69 (10) | O2—C21—H21A | 110.7 |
C35—Pd1—C34 | 34.13 (13) | C22—C21—H21A | 110.7 |
C36—Pd1—C34 | 66.73 (14) | O2—C21—H21B | 110.7 |
C36—Pd1—C35 | 37.64 (14) | C22—C21—H21B | 110.7 |
C36—Pd1—N1 | 169.75 (11) | H21A—C21—H21B | 108.8 |
C36—Pd1—P1 | 102.81 (10) | N2—C22—C21 | 103.6 (3) |
N1—Pd1—C35 | 132.15 (13) | N2—C22—C23 | 111.8 (3) |
N1—Pd1—C34 | 104.20 (12) | C21—C22—C23 | 116.1 (3) |
N1—Pd1—P1 | 87.10 (6) | N2—C22—H22A | 108.3 |
C27—P1—C14 | 102.72 (14) | C21—C22—H22A | 108.3 |
C27—P1—C1 | 102.70 (11) | C23—C22—H22A | 108.3 |
C14—P1—C1 | 104.82 (12) | C24—C23—C25 | 108.9 (3) |
C27—P1—Pd1 | 112.69 (10) | C24—C23—C22 | 109.7 (3) |
C14—P1—Pd1 | 122.01 (9) | C25—C23—C22 | 110.0 (3) |
C1—P1—Pd1 | 109.94 (8) | C24—C23—C26 | 109.0 (4) |
C7—N1—C9 | 107.0 (2) | C25—C23—C26 | 110.1 (4) |
C7—N1—Pd1 | 129.15 (19) | C22—C23—C26 | 109.2 (3) |
C9—N1—Pd1 | 123.8 (2) | C23—C24—H24A | 109.5 |
C20—N2—C22 | 108.0 (3) | C23—C24—H24B | 109.5 |
C7—O1—C8 | 106.1 (2) | H24A—C24—H24B | 109.5 |
C20—O2—C21 | 105.1 (3) | C23—C24—H24C | 109.5 |
C2—C1—C6 | 118.6 (2) | H24A—C24—H24C | 109.5 |
C2—C1—P1 | 119.3 (2) | H24B—C24—H24C | 109.5 |
C6—C1—P1 | 122.0 (2) | C23—C25—H25A | 109.5 |
C1—C2—C3 | 121.3 (3) | C23—C25—H25B | 109.5 |
C1—C2—H2A | 119.4 | H25A—C25—H25B | 109.5 |
C3—C2—H2A | 119.4 | C23—C25—H25C | 109.5 |
C4—C3—C2 | 120.0 (3) | H25A—C25—H25C | 109.5 |
C4—C3—H3A | 120.0 | H25B—C25—H25C | 109.5 |
C2—C3—H3A | 120.0 | C23—C26—H26A | 109.5 |
C3—C4—C5 | 119.7 (3) | C23—C26—H26B | 109.5 |
C3—C4—H4A | 120.1 | H26A—C26—H26B | 109.5 |
C5—C4—H4A | 120.1 | C23—C26—H26C | 109.5 |
C4—C5—C6 | 121.9 (3) | H26A—C26—H26C | 109.5 |
C4—C5—H5A | 119.0 | H26B—C26—H26C | 109.5 |
C6—C5—H5A | 119.0 | C28—C27—C32 | 119.3 (3) |
C1—C6—C5 | 118.4 (3) | C28—C27—P1 | 123.7 (2) |
C1—C6—C7 | 124.9 (2) | C32—C27—P1 | 117.0 (2) |
C5—C6—C7 | 116.6 (3) | C27—C28—C29 | 120.3 (3) |
N1—C7—O1 | 116.8 (2) | C27—C28—H28A | 119.9 |
N1—C7—C6 | 129.4 (2) | C29—C28—H28A | 119.9 |
O1—C7—C6 | 113.8 (2) | C30—C29—C28 | 119.8 (3) |
O1—C8—C9 | 104.5 (3) | C30—C29—H29A | 120.1 |
O1—C8—H8A | 110.8 | C28—C29—H29A | 120.1 |
C9—C8—H8A | 110.8 | C31—C30—C29 | 120.2 (3) |
O1—C8—H8B | 110.8 | C31—C30—H30A | 119.9 |
C9—C8—H8B | 110.8 | C29—C30—H30A | 119.9 |
H8A—C8—H8B | 108.9 | C30—C31—C32 | 120.2 (4) |
N1—C9—C8 | 101.6 (3) | C30—C31—H31A | 119.9 |
N1—C9—C10 | 112.6 (3) | C32—C31—H31A | 119.9 |
C8—C9—C10 | 116.0 (3) | C27—C32—C31 | 120.1 (3) |
N1—C9—H9A | 108.8 | C27—C32—H32A | 119.9 |
C8—C9—H9A | 108.8 | C31—C32—H32A | 119.9 |
C10—C9—H9A | 108.8 | C34—C33—H33A | 109.5 |
C11—C10—C9 | 111.2 (3) | C34—C33—H33B | 109.5 |
C11—C10—C12 | 110.1 (4) | H33A—C33—H33B | 109.5 |
C9—C10—C12 | 111.3 (3) | C34—C33—H33C | 109.5 |
C11—C10—C13 | 108.4 (4) | H33A—C33—H33C | 109.5 |
C9—C10—C13 | 106.5 (4) | H33B—C33—H33C | 109.5 |
C12—C10—C13 | 109.2 (3) | C35—C34—C33 | 136.0 (5) |
C10—C11—H11A | 109.5 | C35—C34—Pd1 | 68.06 (18) |
C10—C11—H11B | 109.5 | C33—C34—Pd1 | 128.9 (3) |
H11A—C11—H11B | 109.5 | C35—C34—H34A | 112.0 |
C10—C11—H11C | 109.5 | C33—C34—H34A | 112.0 |
H11A—C11—H11C | 109.5 | Pd1—C34—H34A | 70.1 |
H11B—C11—H11C | 109.5 | C34—C35—C36 | 128.6 (4) |
C10—C12—H12A | 109.5 | C34—C35—Pd1 | 77.81 (19) |
C10—C12—H12B | 109.5 | C36—C35—Pd1 | 69.81 (17) |
H12A—C12—H12B | 109.5 | C34—C35—H35A | 115.7 |
C10—C12—H12C | 109.5 | C36—C35—H35A | 115.7 |
H12A—C12—H12C | 109.5 | Pd1—C35—H35A | 129.9 |
H12B—C12—H12C | 109.5 | C35—C36—C37 | 126.1 (4) |
C10—C13—H13A | 109.5 | C35—C36—Pd1 | 72.55 (18) |
C10—C13—H13B | 109.5 | C37—C36—Pd1 | 122.0 (3) |
H13A—C13—H13B | 109.5 | C35—C36—H36A | 117.0 |
C10—C13—H13C | 109.5 | C37—C36—H36A | 117.0 |
H13A—C13—H13C | 109.5 | Pd1—C36—H36A | 75.3 |
H13B—C13—H13C | 109.5 | C36—C37—H37A | 109.5 |
C19—C14—C15 | 118.0 (3) | C36—C37—H37B | 109.5 |
C19—C14—P1 | 122.9 (2) | H37A—C37—H37B | 109.5 |
C15—C14—P1 | 118.9 (2) | C36—C37—H37C | 109.5 |
C16—C15—C14 | 121.4 (3) | H37A—C37—H37C | 109.5 |
C16—C15—H15A | 119.3 | H37B—C37—H37C | 109.5 |
C14—C15—H15A | 119.3 | F3—P2—F6 | 88.1 (3) |
C17—C16—C15 | 120.0 (3) | F3—P2—F2 | 89.5 (3) |
C17—C16—H16A | 120.0 | F6—P2—F2 | 91.1 (3) |
C15—C16—H16A | 120.0 | F3—P2—F1 | 91.6 (3) |
C16—C17—C18 | 119.9 (3) | F6—P2—F1 | 90.3 (2) |
C16—C17—H17A | 120.0 | F2—P2—F1 | 178.2 (2) |
C18—C17—H17A | 120.0 | F3—P2—F4 | 91.4 (2) |
C17—C18—C19 | 120.9 (3) | F6—P2—F4 | 179.4 (3) |
C17—C18—H18A | 119.5 | F2—P2—F4 | 89.2 (2) |
C19—C18—H18A | 119.5 | F1—P2—F4 | 89.42 (19) |
C14—C19—C18 | 119.5 (3) | F3—P2—F5 | 177.6 (3) |
C14—C19—C20 | 122.4 (3) | F6—P2—F5 | 94.1 (3) |
C18—C19—C20 | 118.0 (3) | F2—P2—F5 | 91.3 (3) |
N2—C20—O2 | 118.0 (3) | F1—P2—F5 | 87.5 (2) |
N2—C20—C19 | 126.3 (3) | F4—P2—F5 | 86.4 (2) |
O2—C20—C19 | 115.7 (3) | ||
Pd1—P1—C14—C19 | 38.6 (3) | C14—C19—C20—N2 | 17.4 (5) |
Pd1—N1—C9—C10 | 73.1 (3) |
[PdCl2(C32H37N2O2P)] | F(000) = 1416 |
Mr = 689.91 | Dx = 1.469 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 982 reflections |
a = 10.2172 (13) Å | θ = 1.8–27.4° |
b = 13.3580 (18) Å | µ = 0.85 mm−1 |
c = 22.858 (3) Å | T = 83 K |
V = 3119.7 (7) Å3 | Block, orange |
Z = 4 | 0.1 × 0.05 × 0.05 mm |
Bruker SMART APEX CCD diffractometer | 6600 reflections with I > 2σ(I) |
Radiation source: sealed tube | Rint = 0.041 |
Graphite monochromator | θmax = 27.9°, θmin = 1.8° |
Detector resolution: 66 pixels mm-1 | h = −13→12 |
ω scans | k = −12→17 |
20046 measured reflections | l = −25→29 |
7214 independent reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.036 | H-atom parameters constrained |
wR(F2) = 0.091 | w = 1/[σ2(Fo2) + (0.0419P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
7214 reflections | Δρmax = 0.76 e Å−3 |
369 parameters | Δρmin = −0.62 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 3090 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.00 (3) |
[PdCl2(C32H37N2O2P)] | V = 3119.7 (7) Å3 |
Mr = 689.91 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 10.2172 (13) Å | µ = 0.85 mm−1 |
b = 13.3580 (18) Å | T = 83 K |
c = 22.858 (3) Å | 0.1 × 0.05 × 0.05 mm |
Bruker SMART APEX CCD diffractometer | 6600 reflections with I > 2σ(I) |
20046 measured reflections | Rint = 0.041 |
7214 independent reflections |
R[F2 > 2σ(F2)] = 0.036 | H-atom parameters constrained |
wR(F2) = 0.091 | Δρmax = 0.76 e Å−3 |
S = 1.05 | Δρmin = −0.62 e Å−3 |
7214 reflections | Absolute structure: Flack (1983), 3090 Friedel pairs |
369 parameters | Absolute structure parameter: 0.00 (3) |
0 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
Pd1 | 0.86830 (3) | 0.82456 (2) | 0.139380 (13) | 0.01196 (8) | |
Cl1 | 1.01588 (10) | 0.77328 (8) | 0.06486 (5) | 0.0205 (2) | |
Cl2 | 1.02228 (10) | 0.92498 (8) | 0.18350 (5) | 0.0199 (2) | |
P1 | 0.71404 (10) | 0.89032 (8) | 0.19578 (5) | 0.0116 (2) | |
N1 | 0.7350 (3) | 0.7217 (2) | 0.11079 (14) | 0.0132 (7) | |
O1 | 0.5497 (3) | 0.6505 (2) | 0.07988 (13) | 0.0178 (7) | |
N2 | 0.7715 (4) | 1.0187 (3) | 0.09724 (15) | 0.0176 (8) | |
O2 | 0.9151 (3) | 1.1463 (2) | 0.10798 (13) | 0.0245 (8) | |
C1 | 0.5573 (4) | 0.8897 (3) | 0.15790 (17) | 0.0125 (8) | |
C2 | 0.4648 (4) | 0.9629 (3) | 0.17109 (19) | 0.0161 (9) | |
H2A | 0.4857 | 1.0134 | 0.1975 | 0.019* | |
C3 | 0.3425 (4) | 0.9613 (3) | 0.14547 (19) | 0.0175 (9) | |
H3A | 0.2808 | 1.0094 | 0.1558 | 0.021* | |
C4 | 0.3109 (4) | 0.8890 (3) | 0.10481 (19) | 0.0177 (9) | |
H4A | 0.2289 | 0.8895 | 0.0871 | 0.021* | |
C5 | 0.4006 (4) | 0.8161 (3) | 0.09032 (18) | 0.0168 (9) | |
H5A | 0.3791 | 0.7678 | 0.0626 | 0.020* | |
C6 | 0.5245 (4) | 0.8143 (3) | 0.11728 (17) | 0.0139 (8) | |
C7 | 0.6106 (4) | 0.7302 (3) | 0.10323 (17) | 0.0141 (8) | |
C8 | 0.6529 (4) | 0.5840 (3) | 0.06001 (19) | 0.0195 (9) | |
H8A | 0.6675 | 0.5914 | 0.0183 | 0.023* | |
H8B | 0.6311 | 0.5147 | 0.0683 | 0.023* | |
C9 | 0.7729 (4) | 0.6166 (3) | 0.09461 (19) | 0.0165 (9) | |
H9A | 0.8599 | 0.6196 | 0.0688 | 0.017 (11)* | |
C10 | 0.8070 (4) | 0.5503 (3) | 0.1482 (2) | 0.0192 (10) | |
C11 | 0.9277 (4) | 0.5913 (3) | 0.1798 (2) | 0.0255 (11) | |
H11A | 0.9077 | 0.6557 | 0.1961 | 0.038* | |
H11B | 0.9985 | 0.5978 | 0.1524 | 0.038* | |
H11C | 0.9526 | 0.5463 | 0.2105 | 0.038* | |
C12 | 0.6922 (5) | 0.5431 (4) | 0.1911 (2) | 0.0279 (11) | |
H12A | 0.7155 | 0.4998 | 0.2230 | 0.042* | |
H12B | 0.6171 | 0.5165 | 0.1713 | 0.042* | |
H12C | 0.6722 | 0.6086 | 0.2060 | 0.042* | |
C13 | 0.8395 (5) | 0.4446 (3) | 0.1252 (2) | 0.0301 (12) | |
H13A | 0.9036 | 0.4494 | 0.0946 | 0.045* | |
H13B | 0.7615 | 0.4140 | 0.1102 | 0.045* | |
H13C | 0.8737 | 0.4046 | 0.1566 | 0.045* | |
C14 | 0.7333 (4) | 1.0177 (3) | 0.22476 (18) | 0.0118 (8) | |
C15 | 0.6984 (4) | 1.0363 (3) | 0.28255 (18) | 0.0149 (9) | |
H15A | 0.6622 | 0.9848 | 0.3046 | 0.018* | |
C16 | 0.7161 (4) | 1.1293 (3) | 0.30810 (18) | 0.0178 (9) | |
H16A | 0.6888 | 1.1403 | 0.3464 | 0.021* | |
C17 | 0.7743 (4) | 1.2060 (3) | 0.2767 (2) | 0.0201 (10) | |
H17A | 0.7897 | 1.2678 | 0.2941 | 0.024* | |
C18 | 0.8094 (4) | 1.1892 (3) | 0.21883 (19) | 0.0178 (9) | |
H18A | 0.8482 | 1.2405 | 0.1975 | 0.021* | |
C19 | 0.7877 (4) | 1.0971 (3) | 0.19215 (18) | 0.0147 (9) | |
C20 | 0.8216 (4) | 1.0836 (3) | 0.13020 (18) | 0.0159 (9) | |
C21 | 0.9397 (5) | 1.1090 (4) | 0.0492 (2) | 0.0336 (12) | |
H21A | 1.0271 | 1.0812 | 0.0462 | 0.040* | |
H21B | 0.9303 | 1.1621 | 0.0206 | 0.040* | |
C22 | 0.8358 (4) | 1.0275 (3) | 0.03976 (19) | 0.0201 (10) | |
H22A | 0.8811 | 0.9593 | 0.0274 | 0.024 (12)* | |
C23 | 0.7349 (5) | 1.0481 (3) | −0.00901 (19) | 0.0201 (10) | |
C24 | 0.6383 (6) | 0.9617 (4) | −0.0099 (2) | 0.0406 (14) | |
H24A | 0.5829 | 0.9655 | 0.0240 | 0.061* | |
H24B | 0.6853 | 0.8995 | −0.0095 | 0.061* | |
H24C | 0.5857 | 0.9656 | −0.0446 | 0.061* | |
C25 | 0.8070 (5) | 1.0517 (4) | −0.0674 (2) | 0.0303 (11) | |
H25A | 0.7448 | 1.0593 | −0.0986 | 0.045* | |
H25B | 0.8552 | 0.9907 | −0.0728 | 0.045* | |
H25C | 0.8664 | 1.1074 | −0.0676 | 0.045* | |
C26 | 0.6635 (5) | 1.1471 (4) | 0.0008 (2) | 0.0322 (13) | |
H26A | 0.6001 | 1.1569 | −0.0296 | 0.048* | |
H26B | 0.7255 | 1.2010 | 0.0003 | 0.048* | |
H26C | 0.6200 | 1.1455 | 0.0381 | 0.048* | |
C27 | 0.6854 (4) | 0.8154 (3) | 0.26160 (17) | 0.0138 (8) | |
C28 | 0.5599 (4) | 0.7911 (3) | 0.28120 (19) | 0.0185 (9) | |
H28A | 0.4868 | 0.8111 | 0.2599 | 0.022* | |
C29 | 0.5450 (4) | 0.7370 (3) | 0.33267 (19) | 0.0210 (10) | |
H29A | 0.4616 | 0.7209 | 0.3460 | 0.025* | |
C30 | 0.6537 (5) | 0.7070 (3) | 0.3641 (2) | 0.0258 (10) | |
H30A | 0.6430 | 0.6712 | 0.3987 | 0.031* | |
C31 | 0.7782 (5) | 0.7297 (3) | 0.34453 (19) | 0.0236 (10) | |
H31A | 0.8511 | 0.7091 | 0.3658 | 0.028* | |
C32 | 0.7941 (4) | 0.7835 (3) | 0.29300 (19) | 0.0185 (9) | |
H32A | 0.8777 | 0.7983 | 0.2795 | 0.022* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.01024 (13) | 0.01381 (14) | 0.01182 (14) | −0.00132 (12) | 0.00090 (12) | −0.00228 (13) |
Cl1 | 0.0180 (5) | 0.0222 (6) | 0.0213 (6) | −0.0042 (4) | 0.0073 (4) | −0.0078 (4) |
Cl2 | 0.0115 (5) | 0.0224 (6) | 0.0258 (6) | −0.0016 (4) | −0.0010 (4) | −0.0084 (4) |
P1 | 0.0108 (5) | 0.0131 (5) | 0.0109 (5) | −0.0006 (4) | −0.0006 (4) | −0.0009 (4) |
N1 | 0.0168 (18) | 0.0116 (17) | 0.0112 (18) | −0.0013 (14) | 0.0015 (14) | 0.0004 (13) |
O1 | 0.0162 (15) | 0.0159 (17) | 0.0215 (16) | −0.0025 (11) | −0.0010 (12) | −0.0056 (12) |
N2 | 0.0210 (19) | 0.020 (2) | 0.0120 (19) | −0.0025 (15) | −0.0013 (15) | 0.0013 (14) |
O2 | 0.0269 (17) | 0.0301 (19) | 0.0165 (17) | −0.0136 (13) | 0.0038 (13) | 0.0007 (13) |
C1 | 0.0098 (19) | 0.016 (2) | 0.012 (2) | −0.0032 (16) | −0.0003 (15) | 0.0055 (16) |
C2 | 0.013 (2) | 0.017 (2) | 0.019 (2) | −0.0032 (17) | 0.0010 (17) | −0.0008 (17) |
C3 | 0.012 (2) | 0.019 (2) | 0.021 (2) | 0.0018 (15) | 0.0046 (17) | 0.0018 (18) |
C4 | 0.0123 (19) | 0.023 (2) | 0.018 (2) | −0.0033 (17) | −0.0023 (16) | 0.0088 (18) |
C5 | 0.016 (2) | 0.020 (2) | 0.015 (2) | −0.0050 (17) | −0.0007 (15) | 0.0040 (18) |
C6 | 0.0106 (18) | 0.018 (2) | 0.0131 (19) | −0.0038 (17) | 0.0031 (14) | 0.0027 (16) |
C7 | 0.018 (2) | 0.016 (2) | 0.0082 (19) | −0.0051 (17) | 0.0007 (16) | 0.0019 (15) |
C8 | 0.024 (3) | 0.014 (2) | 0.020 (2) | −0.0008 (18) | 0.0010 (18) | −0.0047 (16) |
C9 | 0.017 (2) | 0.015 (2) | 0.017 (2) | −0.0017 (17) | 0.0055 (17) | −0.0039 (17) |
C10 | 0.018 (2) | 0.016 (2) | 0.023 (3) | 0.0014 (16) | 0.0045 (18) | 0.0036 (18) |
C11 | 0.027 (2) | 0.025 (3) | 0.025 (3) | 0.005 (2) | −0.005 (2) | 0.005 (2) |
C12 | 0.029 (3) | 0.025 (3) | 0.030 (3) | 0.001 (2) | 0.008 (2) | 0.009 (2) |
C13 | 0.038 (3) | 0.015 (2) | 0.037 (3) | 0.0038 (19) | 0.007 (2) | 0.0051 (19) |
C14 | 0.0081 (19) | 0.012 (2) | 0.015 (2) | 0.0016 (15) | −0.0006 (15) | −0.0013 (16) |
C15 | 0.012 (2) | 0.018 (2) | 0.015 (2) | 0.0024 (17) | −0.0004 (16) | 0.0010 (17) |
C16 | 0.020 (2) | 0.023 (2) | 0.010 (2) | 0.0058 (18) | 0.0001 (16) | −0.0040 (17) |
C17 | 0.020 (2) | 0.014 (2) | 0.026 (3) | −0.0013 (17) | −0.0043 (19) | −0.0047 (17) |
C18 | 0.016 (2) | 0.013 (2) | 0.024 (2) | −0.0036 (17) | −0.0004 (17) | 0.0011 (17) |
C19 | 0.011 (2) | 0.019 (2) | 0.014 (2) | 0.0021 (16) | −0.0018 (15) | 0.0035 (16) |
C20 | 0.016 (2) | 0.018 (2) | 0.014 (2) | −0.0007 (16) | −0.0008 (16) | 0.0041 (17) |
C21 | 0.036 (3) | 0.052 (3) | 0.013 (2) | −0.015 (3) | 0.003 (2) | 0.001 (2) |
C22 | 0.025 (3) | 0.022 (2) | 0.013 (2) | −0.0007 (18) | 0.0021 (17) | 0.0016 (18) |
C23 | 0.028 (3) | 0.021 (2) | 0.011 (2) | 0.0003 (19) | −0.0025 (18) | 0.0007 (17) |
C24 | 0.052 (3) | 0.049 (3) | 0.022 (3) | −0.019 (3) | −0.017 (3) | 0.005 (2) |
C25 | 0.045 (3) | 0.028 (3) | 0.018 (3) | 0.008 (2) | 0.001 (2) | 0.002 (2) |
C26 | 0.039 (3) | 0.036 (3) | 0.021 (3) | 0.013 (2) | −0.002 (2) | 0.004 (2) |
C27 | 0.0163 (19) | 0.012 (2) | 0.013 (2) | −0.0012 (17) | 0.0007 (15) | −0.0018 (17) |
C28 | 0.021 (2) | 0.018 (2) | 0.016 (2) | −0.0009 (17) | 0.0016 (18) | 0.0000 (16) |
C29 | 0.027 (2) | 0.017 (2) | 0.019 (2) | −0.0092 (19) | 0.0052 (19) | 0.0002 (18) |
C30 | 0.041 (3) | 0.019 (2) | 0.017 (2) | −0.0022 (19) | 0.002 (2) | 0.0026 (17) |
C31 | 0.031 (3) | 0.022 (2) | 0.018 (2) | 0.005 (2) | −0.0034 (18) | 0.0025 (18) |
C32 | 0.018 (2) | 0.021 (2) | 0.017 (2) | 0.0022 (18) | −0.0007 (17) | −0.0030 (17) |
Pd1—N1 | 2.042 (3) | C13—H13B | 0.9600 |
Pd1—P1 | 2.2177 (11) | C13—H13C | 0.9600 |
Pd1—Cl1 | 2.3758 (11) | C14—C15 | 1.390 (6) |
Pd1—Cl2 | 2.3004 (11) | C14—C19 | 1.410 (5) |
P1—C1 | 1.820 (4) | C15—C16 | 1.385 (6) |
P1—C27 | 1.831 (4) | C15—H15A | 0.9300 |
P1—C14 | 1.837 (4) | C16—C17 | 1.384 (6) |
N1—C7 | 1.288 (5) | C16—H16A | 0.9300 |
N1—C9 | 1.502 (5) | C17—C18 | 1.390 (6) |
O1—C7 | 1.344 (5) | C17—H17A | 0.9300 |
O1—C8 | 1.452 (5) | C18—C19 | 1.390 (6) |
N2—C20 | 1.257 (5) | C18—H18A | 0.9300 |
N2—C22 | 1.474 (5) | C19—C20 | 1.469 (6) |
O2—C20 | 1.369 (5) | C21—C22 | 1.535 (6) |
O2—C21 | 1.454 (5) | C21—H21A | 0.9700 |
C1—C2 | 1.393 (6) | C21—H21B | 0.9700 |
C1—C6 | 1.410 (6) | C22—C23 | 1.543 (6) |
C2—C3 | 1.381 (5) | C22—H22A | 1.0608 |
C2—H2A | 0.9300 | C23—C24 | 1.518 (7) |
C3—C4 | 1.378 (6) | C23—C25 | 1.525 (6) |
C3—H3A | 0.9300 | C23—C26 | 1.527 (6) |
C4—C5 | 1.378 (6) | C24—H24A | 0.9600 |
C4—H4A | 0.9300 | C24—H24B | 0.9600 |
C5—C6 | 1.408 (5) | C24—H24C | 0.9600 |
C5—H5A | 0.9300 | C25—H25A | 0.9600 |
C6—C7 | 1.463 (6) | C25—H25B | 0.9600 |
C8—C9 | 1.523 (6) | C25—H25C | 0.9600 |
C8—H8A | 0.9700 | C26—H26A | 0.9600 |
C8—H8B | 0.9700 | C26—H26B | 0.9600 |
C9—C10 | 1.553 (6) | C26—H26C | 0.9600 |
C9—H9A | 1.0679 | C27—C32 | 1.389 (6) |
C10—C11 | 1.530 (6) | C27—C28 | 1.397 (5) |
C10—C12 | 1.531 (6) | C28—C29 | 1.389 (6) |
C10—C13 | 1.543 (6) | C28—H28A | 0.9300 |
C11—H11A | 0.9600 | C29—C30 | 1.382 (6) |
C11—H11B | 0.9600 | C29—H29A | 0.9300 |
C11—H11C | 0.9600 | C30—C31 | 1.382 (6) |
C12—H12A | 0.9600 | C30—H30A | 0.9300 |
C12—H12B | 0.9600 | C31—C32 | 1.389 (6) |
C12—H12C | 0.9600 | C31—H31A | 0.9300 |
C13—H13A | 0.9600 | C32—H32A | 0.9300 |
Pd1···N2 | 2.938 (4) | ||
Cl1—Pd1—Cl2 | 92.77 (4) | C15—C14—C19 | 118.0 (4) |
N1—Pd1—Cl1 | 89.99 (10) | C15—C14—P1 | 118.7 (3) |
N1—Pd1—Cl2 | 171.42 (10) | C19—C14—P1 | 123.2 (3) |
N1—Pd1—P1 | 88.77 (10) | C16—C15—C14 | 121.8 (4) |
P1—Pd1—Cl1 | 169.14 (4) | C16—C15—H15A | 119.1 |
P1—Pd1—Cl2 | 90.01 (4) | C14—C15—H15A | 119.1 |
C1—P1—C27 | 104.36 (18) | C17—C16—C15 | 120.1 (4) |
C1—P1—C14 | 105.66 (19) | C17—C16—H16A | 120.0 |
C27—P1—C14 | 103.15 (18) | C15—C16—H16A | 120.0 |
C1—P1—Pd1 | 110.29 (14) | C16—C17—C18 | 119.0 (4) |
C27—P1—Pd1 | 112.00 (14) | C16—C17—H17A | 120.5 |
C14—P1—Pd1 | 120.04 (13) | C18—C17—H17A | 120.5 |
C7—N1—C9 | 107.7 (3) | C17—C18—C19 | 121.3 (4) |
C7—N1—Pd1 | 129.9 (3) | C17—C18—H18A | 119.3 |
C9—N1—Pd1 | 122.4 (3) | C19—C18—H18A | 119.3 |
C7—O1—C8 | 105.8 (3) | C18—C19—C14 | 119.7 (4) |
C20—N2—C22 | 107.3 (4) | C18—C19—C20 | 119.6 (4) |
C20—O2—C21 | 104.7 (3) | C14—C19—C20 | 120.7 (4) |
C2—C1—C6 | 118.8 (4) | N2—C20—O2 | 118.9 (4) |
C2—C1—P1 | 119.4 (3) | N2—C20—C19 | 124.5 (4) |
C6—C1—P1 | 121.7 (3) | O2—C20—C19 | 116.6 (4) |
C3—C2—C1 | 120.8 (4) | O2—C21—C22 | 104.7 (4) |
C3—C2—H2A | 119.6 | O2—C21—H21A | 110.8 |
C1—C2—H2A | 119.6 | C22—C21—H21A | 110.8 |
C4—C3—C2 | 120.6 (4) | O2—C21—H21B | 110.8 |
C4—C3—H3A | 119.7 | C22—C21—H21B | 110.8 |
C2—C3—H3A | 119.7 | H21A—C21—H21B | 108.9 |
C5—C4—C3 | 120.1 (4) | N2—C22—C21 | 103.8 (3) |
C5—C4—H4A | 119.9 | N2—C22—C23 | 111.1 (3) |
C3—C4—H4A | 119.9 | C21—C22—C23 | 115.9 (4) |
C4—C5—C6 | 120.3 (4) | N2—C22—H22A | 111.3 |
C4—C5—H5A | 119.9 | C21—C22—H22A | 110.2 |
C6—C5—H5A | 119.9 | C23—C22—H22A | 104.6 |
C5—C6—C1 | 119.4 (4) | C24—C23—C25 | 109.1 (4) |
C5—C6—C7 | 117.2 (4) | C24—C23—C26 | 110.5 (4) |
C1—C6—C7 | 123.3 (4) | C25—C23—C26 | 109.4 (4) |
N1—C7—O1 | 116.1 (4) | C24—C23—C22 | 108.0 (4) |
N1—C7—C6 | 129.2 (4) | C25—C23—C22 | 108.4 (4) |
O1—C7—C6 | 114.7 (3) | C26—C23—C22 | 111.5 (4) |
O1—C8—C9 | 104.3 (3) | C23—C24—H24A | 109.5 |
O1—C8—H8A | 110.9 | C23—C24—H24B | 109.5 |
C9—C8—H8A | 110.9 | H24A—C24—H24B | 109.5 |
O1—C8—H8B | 110.9 | C23—C24—H24C | 109.5 |
C9—C8—H8B | 110.9 | H24A—C24—H24C | 109.5 |
H8A—C8—H8B | 108.9 | H24B—C24—H24C | 109.5 |
N1—C9—C8 | 100.8 (3) | C23—C25—H25A | 109.5 |
N1—C9—C10 | 113.4 (3) | C23—C25—H25B | 109.5 |
C8—C9—C10 | 115.3 (3) | H25A—C25—H25B | 109.5 |
N1—C9—H9A | 108.5 | C23—C25—H25C | 109.5 |
C8—C9—H9A | 113.2 | H25A—C25—H25C | 109.5 |
C10—C9—H9A | 105.7 | H25B—C25—H25C | 109.5 |
C11—C10—C12 | 109.8 (4) | C23—C26—H26A | 109.5 |
C11—C10—C13 | 108.4 (4) | C23—C26—H26B | 109.5 |
C12—C10—C13 | 109.0 (4) | H26A—C26—H26B | 109.5 |
C11—C10—C9 | 110.4 (3) | C23—C26—H26C | 109.5 |
C12—C10—C9 | 111.7 (4) | H26A—C26—H26C | 109.5 |
C13—C10—C9 | 107.6 (4) | H26B—C26—H26C | 109.5 |
C10—C11—H11A | 109.5 | C32—C27—C28 | 119.8 (4) |
C10—C11—H11B | 109.5 | C32—C27—P1 | 117.7 (3) |
H11A—C11—H11B | 109.5 | C28—C27—P1 | 122.5 (3) |
C10—C11—H11C | 109.5 | C29—C28—C27 | 119.5 (4) |
H11A—C11—H11C | 109.5 | C29—C28—H28A | 120.2 |
H11B—C11—H11C | 109.5 | C27—C28—H28A | 120.2 |
C10—C12—H12A | 109.5 | C30—C29—C28 | 120.2 (4) |
C10—C12—H12B | 109.5 | C30—C29—H29A | 119.9 |
H12A—C12—H12B | 109.5 | C28—C29—H29A | 119.9 |
C10—C12—H12C | 109.5 | C31—C30—C29 | 120.5 (4) |
H12A—C12—H12C | 109.5 | C31—C30—H30A | 119.7 |
H12B—C12—H12C | 109.5 | C29—C30—H30A | 119.7 |
C10—C13—H13A | 109.5 | C30—C31—C32 | 119.7 (4) |
C10—C13—H13B | 109.5 | C30—C31—H31A | 120.2 |
H13A—C13—H13B | 109.5 | C32—C31—H31A | 120.2 |
C10—C13—H13C | 109.5 | C27—C32—C31 | 120.2 (4) |
H13A—C13—H13C | 109.5 | C27—C32—H32A | 119.9 |
H13B—C13—H13C | 109.5 | C31—C32—H32A | 119.9 |
Pd1—N1—C9—C10 | 72.7 (4) | Pd1—P1—C14—C19 | 38.8 (4) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Pd(C32H37N2O2P)(C5H9)]PF6 | [PdCl2(C32H37N2O2P)] |
Mr | 833.10 | 689.91 |
Crystal system, space group | Monoclinic, P21 | Orthorhombic, P212121 |
Temperature (K) | 293 | 83 |
a, b, c (Å) | 10.3152 (13), 13.5764 (17), 13.8415 (18) | 10.2172 (13), 13.3580 (18), 22.858 (3) |
α, β, γ (°) | 90, 96.345 (2), 90 | 90, 90, 90 |
V (Å3) | 1926.5 (4) | 3119.7 (7) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.63 | 0.85 |
Crystal size (mm) | 0.8 × 0.4 × 0.4 | 0.1 × 0.05 × 0.05 |
Data collection | ||
Diffractometer | Bruker SMART APEX CCD diffractometer | Bruker SMART APEX CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) | – |
Tmin, Tmax | 0.536, 0.634 | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12103, 8317, 7836 | 20046, 7214, 6600 |
Rint | 0.014 | 0.041 |
(sin θ/λ)max (Å−1) | 0.655 | 0.659 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.074, 1.00 | 0.036, 0.091, 1.05 |
No. of reflections | 8317 | 7214 |
No. of parameters | 459 | 369 |
No. of restraints | 1 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.58, −0.28 | 0.76, −0.62 |
Absolute structure | Flack (1983), 3757 Friedel pairs | Flack (1983), 3090 Friedel pairs |
Absolute structure parameter | 0.001 (17) | 0.00 (3) |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXTL (Bruker, 1997) and PLATON (Spek, 2003), SHELXTL.
Pd1—C34 | 2.271 (3) | Pd1—N1 | 2.125 (2) |
Pd1—C35 | 2.155 (3) | Pd1—P1 | 2.2864 (7) |
Pd1—C36 | 2.120 (3) | ||
C34—Pd1—P1 | 163.33 (12) | C36—Pd1—N1 | 169.75 (11) |
C35—Pd1—P1 | 139.69 (10) | C36—Pd1—P1 | 102.81 (10) |
C35—Pd1—C34 | 34.13 (13) | N1—Pd1—C35 | 132.15 (13) |
C36—Pd1—C34 | 66.73 (14) | N1—Pd1—C34 | 104.20 (12) |
C36—Pd1—C35 | 37.64 (14) | N1—Pd1—P1 | 87.10 (6) |
Pd1—P1—C14—C19 | 38.6 (3) | C14—C19—C20—N2 | 17.4 (5) |
Pd1—N1—C9—C10 | 73.1 (3) |
Pd1—N1 | 2.042 (3) | Pd1—Cl1 | 2.3758 (11) |
Pd1—P1 | 2.2177 (11) | Pd1—Cl2 | 2.3004 (11) |
Cl1—Pd1—Cl2 | 92.77 (4) | N1—Pd1—P1 | 88.77 (10) |
N1—Pd1—Cl1 | 89.99 (10) | P1—Pd1—Cl1 | 169.14 (4) |
N1—Pd1—Cl2 | 171.42 (10) | P1—Pd1—Cl2 | 90.01 (4) |
Pd1—N1—C9—C10 | 72.7 (4) | Pd1—P1—C14—C19 | 38.8 (4) |
The exploration of new chiral phospine ligands has contributed substantially to the development of asymmetric catalysis (Pfaltz, 1999; Gavrilov & Polosukhin, 2000; Muniz & Bolm, 2000; Henry, 2002; Noyori, 2002; Tang et al., 2003). Although many chiral phosphines have been prepared by combining compounds containing achiral P atoms with readily accessible chiral backbones derived from binaphthyl, tartarate, amino acids etc., much attention has recently been directed to phosphines derived from compounds containing pre-existing chiral phosphorus atoms (such as duPHOS, TangPHOS etc.), as the resultant catalysts are effective? in asymmetric catalysis (Burk et al., 1996; Yamanoi & Imamoto, 1999; Albert et al., 2000; Tang & Zhang, 2003). Difficulties associated with the generation of a chiral phosphorus atom during synthesis have long been known, as have the problems encountered in resolving enatiomerically mixed preparations.
The selective coordination of the potential tridentate ligand to a metal ion in a bidentate-κ2B,P manner will generate a new chiral centre on the P atom. In the case of an AB2P-type phosphine ligand, where the B moiety has a ligating atom and A has not, the use of a chiral B moiety can influence the ratio of SP to RP, and the selective ligation system can construct a chiral reaction field around a metal active site imposed by the chiralities of the B and P moieties. Within the scope of this concept, we have engaged in the synthesis of selectively coordinating ligands and have conducted studies on the synthesis, reactivity and catalysis of their selectively coordinated complexes (Yamada et al., 1996; Yamagishi, 1996; Yamada et al., 1997a; Yamada et al., 1997b; Yamagishi et al., 2003).
We have estimated the chirality of the complexes using CD? spectra in a series of earlier studies, although the absolute structures have not yet been determined. We have now obtained single crystals of [{bis((S)-4-tert-butyl-4,5-dihydrooxazol-2-ylphenyl)phenylphoshine- κ2N,P}(1,3-dimethyl-π-allyl-κ3C)palladium(II)] bishexafluorophosphate, (I), and (S)P-[{bis((S)-4-tert-butyl-4,5- dihydrooxazol-2-ylphenyl)phenylphoshine-κ2N,P} dichloropalladium(II)], (II), and investigated their structures, paying particular attention to the chirality around the P atom.
The structure of (I) contains a PdII metal ion, a bis(oxazolyl)phosphine ligand (NPN ligand) and a 1,3-dimethyl-π-allyl group, together with a PF6 counter ion. The P atom and atom N1 of one oxazolyl moiety coordinate to atom Pd1, whereas the second oxazolyl group is uncoordinated. Atoms N1 and P1 and three allylic C atoms (C34–C36) surround atom Pd1 in a distorted square-planar configuration. Both methyl groups (C33 and C37) of the allyl ligand are located syn with respect to atom H35, giving rise to a syn,syn-mode of binding for the 1,3-dimethyl-π-allyl ligand. The chirality of atom P1 is determined to be S from the Flack (1983) parameter, and the use of an S,S-ligand ensures ?a similar chirality? for atoms C9 and C22. The Pd1—C34 distance is longer than the Pd1—C36 distance because of the trans influence of atoms P1 and N1. The C14—C19—C20—N2 torsion angle may be influenced by steric congestion between the C23–C26 tert-butyl goup and other parts of the complex. The second uncoordinated oxazole moiety appears on the opposite side of the Pd—P1—N1 plane relative to the tert-butyl group of the coordinated oxazole moiety.
There are earlier crystallographic reports on bidentate-κ2NP diphenylphosphino-4-substituted-4,5-dihydrooxazole complexes of π-allyl palladium, such as the tert-butyl 4-substituent (Bernardinelli et al., 2001; Kollmar et al., 2001) and other alkyl and phenyl 4-substituents (Baltzer et al., 1996; Schaffner et al., 1997; Schaffner et al., 1998; Sprinz et al., 1994). Among these examples, Kollmar reported [(1,3-diethyl-π-allyl)-((4S)-(2-(2- diphenylphosphino)phenyl)-4,5-dihydro-4-tert-butyloxazole-κ2N,P)- palladium(II)] (Kollmar et al., 2001). The P1—Pd1—N1 and C34—Pd1—C36 angles, and the Pd1—P1, Pd1—N1, Pd1—C34, Pd1—C35 and Pd1—C36 distances in (I) are similar to the equivalent angles and distances in structure determined by Kollmar et al. (2001) [P—Pd—N = 87.46 (9) °, C—Pd—C = 68.2 (2) Å, Pd—P = 2.2816 (10) Å, Pd—N = 2.112 (4) Å, and Pd—C = 2.261 (5), 2.164 (4) and 2.114 (5) Å]. These similarities show that the uncoordinated oxazolyl group in (I) has little influence on the coordination of the NPN ligand; it remains a bidentate-κ2N,P ligand and simply behaves as a large substituent on one of the phenyl groups attached to the P atom.
The NPN ligand in (II), like that in I, ligates to palladium chloride in a bidentate-κ2N,P manner. Atoms P1, N1, Cl1 and Cl2 complete a distorted square-planar configuration around atom Pd1. The chirality at atoms P1, C15 and C27 is determined to be S from the Flack (1983) parameter. The Pd1—Cl2 distance is longer than Pd1—Cl1 because of the trans influence, as described above for (I). The structures of the NPN ligand in (I) and (II) hardly differ, although they have different ligands (1,3-dimethyl-π-allyl and dichloride, respectively). The Pd1···N2 distance [2.938 (4) Å] to the non-coordinated oxazolyl group is slightly shorter in (II) than it is in (I) [3.108 (3) Å]. The Pd1—P1—C14—C19 and Pd1—N1—C9—C10 torsion angles are similar in the two compounds.