Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107052742/hj3055sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107052742/hj3055Isup2.hkl |
CCDC reference: 672407
For related literature, see: Allen (2002); Atkinson et al. (2004); Balavoine et al. (1998); Colacot (2003); Flack (1983); García Mancheño, Gómez Arrayás & Carretero (2005); Gomez Arrayas, Adrio & Carretero (2006); Jacobsen et al. (1999); Le Roux, Malacea, Manoury, Poli, Gonsalvi & Peruzzini (2007); Malacea et al. (2007); Malacea, Daran, Duckett, Dunne, Manoury, Poli & Withwood (2006); Malacea, Manoury, Routaboul, Daran, Poli, Dunne, Withwood, Godard & Duckett (2006); Mateus et al. (2006); Noyori (1994); Ojima (2000); Riant & Kagan (1997); Richards & Locke (1998); Routaboul et al. (2005, 2007); Steiner (1998); Togni (1996).
Thioether (S)-2 (88 mg, 0.225 mmol) and [PdCl2(CH3CN)2] (58 mg, 0.225 mmol) were dissolved in dry dichloromethane (15 ml) under argon. After stirring for 2 h at room temperature, the solvent was evaporated and the resulting red solid was washed with dry pentane (yield 113 mg, 81%). Single crystals of complex (I) were obtained by slow evaporation of a methanol solution and used for structural studies by X-ray diffraction. Spectroscopic analysis: 1H NMR (500 MHz, CDCl3, δ, p.p.m.): 7.72–7.53 (6H, m, Ph), 751–7.41 (4H, m, Ph), 4.63 (5H, s, Cp), 4.56 (1H, s large, subst. Cp), 4.41 (1H, s large, subst. Cp), 3.78 [1H, d(AB), JHH = 12 Hz, CH2—Cp], 3.53 (1H, s large, subst. Cp), 3.29 (1H, d, JHH = 12 Hz, CH2—Cp), 3.24 (2H, q, JHH = 7 Hz, CH2—CH3), 1.38 (3H, t, JHH = 7 Hz, CH2—CH3). 31P NMR (500 MHz, CDCl3, δ, p.p.m.): 21.2. [Please clarify the meaning of the 2 in the text underneath the arrow]
All H atoms were fixed geometrically and treated as riding, with C—H = 0.93 (aromatic), 0.96 (methyl) or 0.97 Å (methylene), and with Uiso(H) = 1.2Ueq(Caromatic or Cmethylene) or 1.5Ueq(Cmethyl).
Data collection: IPDS Software (Stoe & Cie, 2000); cell refinement: IPDS Software (Stoe & Cie, 2000); data reduction: X-RED (Stoe & Cie, 1996); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
[PdFe(C5H5)(C20H20PS)Cl2] | F(000) = 1248 |
Mr = 621.63 | Dx = 1.678 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 8000 reflections |
a = 9.7644 (7) Å | θ = 1.7–26.2° |
b = 14.8595 (15) Å | µ = 1.70 mm−1 |
c = 16.9586 (12) Å | T = 180 K |
V = 2460.6 (4) Å3 | Plate, orange |
Z = 4 | 0.58 × 0.31 × 0.1 mm |
Stoe IPDS diffractometer | 4771 independent reflections |
Radiation source: fine-focus sealed tube | 4539 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.045 |
ϕ scans | θmax = 26.0°, θmin = 2.4° |
Absorption correction: multi-scan (Blessing, 1995) | h = −11→11 |
Tmin = 0.565, Tmax = 0.856 | k = −18→18 |
24267 measured reflections | l = −20→20 |
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)] = 0.024 | H-atom parameters constrained |
wR(F2) = 0.059 | w = 1/[σ2(Fo2) + (0.0416P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
4771 reflections | Δρmax = 0.51 e Å−3 |
281 parameters | Δρmin = −0.53 e Å−3 |
0 restraints | Absolute structure: Flack (1983), with 2048 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.008 (17) |
[PdFe(C5H5)(C20H20PS)Cl2] | V = 2460.6 (4) Å3 |
Mr = 621.63 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 9.7644 (7) Å | µ = 1.70 mm−1 |
b = 14.8595 (15) Å | T = 180 K |
c = 16.9586 (12) Å | 0.58 × 0.31 × 0.1 mm |
Stoe IPDS diffractometer | 4771 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 4539 reflections with I > 2σ(I) |
Tmin = 0.565, Tmax = 0.856 | Rint = 0.045 |
24267 measured reflections |
R[F2 > 2σ(F2)] = 0.024 | H-atom parameters constrained |
wR(F2) = 0.059 | Δρmax = 0.51 e Å−3 |
S = 1.04 | Δρmin = −0.53 e Å−3 |
4771 reflections | Absolute structure: Flack (1983), with 2048 Friedel pairs |
281 parameters | Absolute structure parameter: −0.008 (17) |
0 restraints |
Experimental. The data were collected on a Stoe Imaging Plate Diffraction System (IPDS). The crystal-to-detector distance was 70 mm. 167 frames (2 min per frame) were obtained with 0 < ϕ < 250.5° and with the crystals rotated through 1.5° in ϕ. Coverage of the unique set was over 99.3% complete to at least 25.95°. Crystal decay was monitored by measuring 200 reflections per frame. |
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 | 0.76139 (2) | 0.738713 (13) | 0.355914 (11) | 0.02042 (6) | |
Fe1 | 0.43968 (5) | 0.62482 (3) | 0.22514 (2) | 0.02661 (10) | |
Cl1 | 0.75407 (9) | 0.86456 (4) | 0.44174 (4) | 0.03110 (15) | |
Cl2 | 0.94560 (9) | 0.79663 (6) | 0.28866 (4) | 0.03622 (18) | |
P1 | 0.77471 (8) | 0.61289 (5) | 0.28463 (4) | 0.02128 (15) | |
S2 | 0.56953 (8) | 0.69480 (5) | 0.42409 (4) | 0.02629 (16) | |
C1 | 0.6126 (3) | 0.56317 (19) | 0.26518 (17) | 0.0244 (6) | |
C2 | 0.5034 (3) | 0.5549 (2) | 0.32195 (18) | 0.0255 (6) | |
C3 | 0.3940 (3) | 0.5087 (2) | 0.2850 (2) | 0.0340 (7) | |
H3 | 0.3109 | 0.4941 | 0.3085 | 0.041* | |
C4 | 0.4319 (3) | 0.4884 (2) | 0.2062 (2) | 0.0345 (7) | |
H4 | 0.3777 | 0.4587 | 0.1694 | 0.041* | |
C5 | 0.5655 (3) | 0.5210 (2) | 0.19317 (18) | 0.0309 (7) | |
H5 | 0.6148 | 0.5162 | 0.1465 | 0.037* | |
C6 | 0.3554 (4) | 0.7456 (3) | 0.2582 (2) | 0.0517 (10) | |
H6 | 0.3434 | 0.7662 | 0.3095 | 0.062* | |
C7 | 0.4706 (4) | 0.7604 (2) | 0.2105 (2) | 0.0429 (8) | |
H7 | 0.5484 | 0.7925 | 0.2250 | 0.051* | |
C8 | 0.4486 (4) | 0.7185 (2) | 0.1370 (2) | 0.0397 (8) | |
H8 | 0.5091 | 0.7179 | 0.0946 | 0.048* | |
C9 | 0.3183 (4) | 0.6775 (3) | 0.1392 (2) | 0.0437 (8) | |
H9 | 0.2779 | 0.6454 | 0.0983 | 0.052* | |
C10 | 0.2597 (4) | 0.6931 (3) | 0.2139 (2) | 0.0512 (9) | |
H10 | 0.1746 | 0.6731 | 0.2312 | 0.061* | |
C21 | 0.5150 (3) | 0.5796 (2) | 0.40670 (17) | 0.0293 (7) | |
H21A | 0.5799 | 0.5393 | 0.4317 | 0.035* | |
H21B | 0.4268 | 0.5706 | 0.4317 | 0.035* | |
C111 | 0.8553 (3) | 0.6158 (2) | 0.18850 (17) | 0.0262 (6) | |
C112 | 0.8135 (3) | 0.6804 (2) | 0.13394 (18) | 0.0331 (7) | |
H112 | 0.7516 | 0.7249 | 0.1488 | 0.040* | |
C113 | 0.8641 (4) | 0.6783 (2) | 0.05782 (19) | 0.0401 (8) | |
H113 | 0.8333 | 0.7200 | 0.0210 | 0.048* | |
C114 | 0.9595 (4) | 0.6150 (2) | 0.0362 (2) | 0.0440 (9) | |
H114 | 0.9943 | 0.6145 | −0.0149 | 0.053* | |
C115 | 1.0032 (4) | 0.5527 (3) | 0.0902 (2) | 0.0430 (9) | |
H115 | 1.0695 | 0.5108 | 0.0758 | 0.052* | |
C116 | 0.9498 (4) | 0.5511 (2) | 0.16617 (19) | 0.0328 (7) | |
H116 | 0.9773 | 0.5070 | 0.2017 | 0.039* | |
C121 | 0.8693 (3) | 0.53105 (19) | 0.34146 (16) | 0.0238 (6) | |
C122 | 0.8292 (3) | 0.4416 (2) | 0.3467 (2) | 0.0321 (7) | |
H122 | 0.7520 | 0.4218 | 0.3196 | 0.038* | |
C123 | 0.9038 (4) | 0.3819 (2) | 0.3922 (2) | 0.0407 (8) | |
H123 | 0.8771 | 0.3219 | 0.3948 | 0.049* | |
C124 | 1.0153 (4) | 0.4097 (3) | 0.4329 (2) | 0.0452 (9) | |
H124 | 1.0633 | 0.3692 | 0.4643 | 0.054* | |
C125 | 1.0585 (4) | 0.4991 (2) | 0.4280 (2) | 0.0448 (9) | |
H125 | 1.1360 | 0.5181 | 0.4552 | 0.054* | |
C126 | 0.9852 (4) | 0.5589 (2) | 0.3824 (2) | 0.0362 (8) | |
H126 | 1.0136 | 0.6185 | 0.3789 | 0.043* | |
C211 | 0.6203 (4) | 0.6833 (2) | 0.52697 (19) | 0.0385 (8) | |
H21C | 0.6322 | 0.7431 | 0.5489 | 0.046* | |
H21D | 0.5460 | 0.6548 | 0.5555 | 0.046* | |
C212 | 0.7498 (4) | 0.6301 (3) | 0.54188 (19) | 0.0448 (8) | |
H21E | 0.7430 | 0.5725 | 0.5166 | 0.067* | |
H21F | 0.7618 | 0.6218 | 0.5976 | 0.067* | |
H21G | 0.8269 | 0.6623 | 0.5209 | 0.067* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.02368 (11) | 0.01917 (10) | 0.01840 (10) | 0.00079 (8) | 0.00063 (8) | −0.00069 (7) |
Fe1 | 0.0261 (2) | 0.0299 (2) | 0.0239 (2) | 0.00386 (18) | −0.00407 (17) | −0.00172 (17) |
Cl1 | 0.0380 (4) | 0.0247 (3) | 0.0306 (3) | 0.0039 (4) | −0.0024 (3) | −0.0072 (3) |
Cl2 | 0.0399 (4) | 0.0385 (4) | 0.0303 (4) | −0.0135 (3) | 0.0107 (3) | −0.0050 (3) |
P1 | 0.0241 (4) | 0.0203 (3) | 0.0194 (3) | 0.0010 (3) | 0.0004 (3) | −0.0018 (3) |
S2 | 0.0254 (4) | 0.0317 (4) | 0.0218 (3) | −0.0008 (3) | 0.0036 (3) | −0.0024 (3) |
C1 | 0.0268 (15) | 0.0220 (13) | 0.0243 (14) | 0.0035 (11) | −0.0016 (12) | −0.0011 (11) |
C2 | 0.0249 (15) | 0.0256 (15) | 0.0259 (15) | −0.0018 (12) | −0.0022 (12) | −0.0001 (12) |
C3 | 0.0315 (17) | 0.0341 (17) | 0.0365 (18) | −0.0060 (13) | −0.0029 (14) | −0.0008 (14) |
C4 | 0.0355 (18) | 0.0305 (16) | 0.0376 (17) | −0.0032 (14) | −0.0108 (15) | −0.0088 (14) |
C5 | 0.0363 (17) | 0.0298 (16) | 0.0267 (15) | 0.0043 (14) | −0.0064 (14) | −0.0101 (12) |
C6 | 0.065 (3) | 0.046 (2) | 0.043 (2) | 0.033 (2) | −0.0043 (18) | −0.0052 (17) |
C7 | 0.051 (2) | 0.0287 (17) | 0.049 (2) | 0.0099 (16) | −0.0165 (17) | 0.0005 (15) |
C8 | 0.0422 (18) | 0.0410 (19) | 0.0359 (18) | 0.0071 (15) | −0.0075 (16) | 0.0081 (15) |
C9 | 0.0380 (18) | 0.053 (2) | 0.0402 (19) | 0.0085 (16) | −0.0152 (17) | 0.0045 (18) |
C10 | 0.0341 (19) | 0.066 (2) | 0.054 (2) | 0.020 (2) | −0.0009 (19) | 0.0091 (19) |
C21 | 0.0324 (17) | 0.0349 (18) | 0.0208 (15) | −0.0073 (13) | 0.0009 (12) | 0.0013 (13) |
C111 | 0.0251 (15) | 0.0278 (15) | 0.0258 (14) | −0.0054 (12) | 0.0011 (12) | −0.0020 (12) |
C112 | 0.0443 (18) | 0.0304 (16) | 0.0245 (16) | −0.0001 (13) | 0.0039 (14) | −0.0007 (13) |
C113 | 0.059 (2) | 0.0350 (18) | 0.0263 (16) | −0.0098 (16) | 0.0043 (16) | 0.0015 (14) |
C114 | 0.063 (3) | 0.0385 (19) | 0.0299 (17) | −0.0136 (18) | 0.0147 (17) | −0.0118 (15) |
C115 | 0.046 (2) | 0.045 (2) | 0.0387 (19) | −0.0033 (16) | 0.0148 (16) | −0.0206 (17) |
C116 | 0.0362 (18) | 0.0313 (17) | 0.0308 (16) | 0.0024 (14) | 0.0026 (14) | −0.0079 (13) |
C121 | 0.0263 (14) | 0.0253 (14) | 0.0199 (13) | 0.0037 (11) | −0.0011 (11) | −0.0028 (11) |
C122 | 0.0351 (17) | 0.0243 (15) | 0.0368 (17) | −0.0032 (12) | −0.0037 (15) | −0.0030 (14) |
C123 | 0.051 (2) | 0.0234 (16) | 0.0472 (19) | 0.0010 (15) | −0.0078 (17) | 0.0055 (15) |
C124 | 0.059 (2) | 0.0352 (19) | 0.0412 (19) | 0.0145 (17) | −0.0171 (18) | 0.0013 (16) |
C125 | 0.046 (2) | 0.039 (2) | 0.050 (2) | 0.0068 (17) | −0.0250 (18) | −0.0081 (16) |
C126 | 0.0382 (19) | 0.0265 (18) | 0.0439 (19) | 0.0001 (14) | −0.0089 (15) | −0.0050 (14) |
C211 | 0.047 (2) | 0.046 (2) | 0.0222 (15) | −0.0106 (17) | 0.0048 (15) | −0.0068 (14) |
C212 | 0.049 (2) | 0.053 (2) | 0.0320 (16) | −0.013 (2) | −0.0146 (17) | 0.0044 (14) |
Pd1—P1 | 2.2302 (7) | C8—H8 | 0.9300 |
Pd1—S2 | 2.2962 (8) | C9—C10 | 1.409 (5) |
Pd1—Cl2 | 2.2971 (8) | C9—H9 | 0.9300 |
Pd1—Cl1 | 2.3708 (7) | C10—H10 | 0.9300 |
Fe1—C9 | 2.034 (3) | C21—H21A | 0.9700 |
Fe1—C1 | 2.037 (3) | C21—H21B | 0.9700 |
Fe1—C10 | 2.038 (4) | C111—C116 | 1.385 (4) |
Fe1—C2 | 2.040 (3) | C111—C112 | 1.395 (4) |
Fe1—C8 | 2.044 (3) | C112—C113 | 1.383 (4) |
Fe1—C5 | 2.045 (3) | C112—H112 | 0.9300 |
Fe1—C3 | 2.050 (3) | C113—C114 | 1.374 (5) |
Fe1—C6 | 2.052 (4) | C113—H113 | 0.9300 |
Fe1—C7 | 2.052 (4) | C114—C115 | 1.371 (6) |
Fe1—C4 | 2.053 (3) | C114—H114 | 0.9300 |
P1—C1 | 1.778 (3) | C115—C116 | 1.391 (5) |
P1—C121 | 1.806 (3) | C115—H115 | 0.9300 |
P1—C111 | 1.811 (3) | C116—H116 | 0.9300 |
S2—C21 | 1.816 (3) | C121—C122 | 1.388 (4) |
S2—C211 | 1.822 (3) | C121—C126 | 1.391 (4) |
C1—C2 | 1.442 (4) | C122—C123 | 1.384 (5) |
C1—C5 | 1.448 (4) | C122—H122 | 0.9300 |
C2—C3 | 1.416 (4) | C123—C124 | 1.354 (5) |
C2—C21 | 1.488 (4) | C123—H123 | 0.9300 |
C3—C4 | 1.419 (5) | C124—C125 | 1.396 (6) |
C3—H3 | 0.9300 | C124—H124 | 0.9300 |
C4—C5 | 1.409 (5) | C125—C126 | 1.378 (5) |
C4—H4 | 0.9300 | C125—H125 | 0.9300 |
C5—H5 | 0.9300 | C126—H126 | 0.9300 |
C6—C7 | 1.402 (6) | C211—C212 | 1.513 (6) |
C6—C10 | 1.430 (6) | C211—H21C | 0.9700 |
C6—H6 | 0.9300 | C211—H21D | 0.9700 |
C7—C8 | 1.411 (5) | C212—H21E | 0.9600 |
C7—H7 | 0.9300 | C212—H21F | 0.9600 |
C8—C9 | 1.411 (5) | C212—H21G | 0.9600 |
P1—Pd1—S2 | 94.72 (3) | C4—C5—H5 | 126.0 |
P1—Pd1—Cl2 | 89.96 (3) | C1—C5—H5 | 126.0 |
S2—Pd1—Cl2 | 174.47 (3) | Fe1—C5—H5 | 126.5 |
P1—Pd1—Cl1 | 174.74 (3) | C7—C6—C10 | 107.9 (3) |
S2—Pd1—Cl1 | 83.71 (3) | C7—C6—Fe1 | 70.0 (2) |
Cl2—Pd1—Cl1 | 91.89 (3) | C10—C6—Fe1 | 69.0 (2) |
C9—Fe1—C1 | 153.43 (14) | C7—C6—H6 | 126.1 |
C9—Fe1—C10 | 40.47 (15) | C10—C6—H6 | 126.1 |
C1—Fe1—C10 | 165.82 (14) | Fe1—C6—H6 | 126.5 |
C9—Fe1—C2 | 161.75 (14) | C6—C7—C8 | 108.6 (3) |
C1—Fe1—C2 | 41.42 (12) | C6—C7—Fe1 | 70.0 (2) |
C10—Fe1—C2 | 126.28 (14) | C8—C7—Fe1 | 69.6 (2) |
C9—Fe1—C8 | 40.48 (15) | C6—C7—H7 | 125.7 |
C1—Fe1—C8 | 120.96 (14) | C8—C7—H7 | 125.7 |
C10—Fe1—C8 | 68.25 (16) | Fe1—C7—H7 | 126.3 |
C2—Fe1—C8 | 157.26 (14) | C7—C8—C9 | 107.7 (3) |
C9—Fe1—C5 | 116.75 (14) | C7—C8—Fe1 | 70.2 (2) |
C1—Fe1—C5 | 41.54 (11) | C9—C8—Fe1 | 69.4 (2) |
C10—Fe1—C5 | 150.30 (15) | C7—C8—H8 | 126.2 |
C2—Fe1—C5 | 69.27 (12) | C9—C8—H8 | 126.2 |
C8—Fe1—C5 | 107.09 (14) | Fe1—C8—H8 | 125.9 |
C9—Fe1—C3 | 123.44 (15) | C10—C9—C8 | 108.6 (4) |
C1—Fe1—C3 | 68.72 (13) | C10—C9—Fe1 | 69.9 (2) |
C10—Fe1—C3 | 106.12 (16) | C8—C9—Fe1 | 70.14 (19) |
C2—Fe1—C3 | 40.50 (12) | C10—C9—H9 | 125.7 |
C8—Fe1—C3 | 160.70 (13) | C8—C9—H9 | 125.7 |
C5—Fe1—C3 | 68.12 (14) | Fe1—C9—H9 | 125.8 |
C9—Fe1—C6 | 68.02 (16) | C9—C10—C6 | 107.3 (4) |
C1—Fe1—C6 | 129.38 (14) | C9—C10—Fe1 | 69.6 (2) |
C10—Fe1—C6 | 40.92 (17) | C6—C10—Fe1 | 70.1 (2) |
C2—Fe1—C6 | 110.36 (14) | C9—C10—H10 | 126.4 |
C8—Fe1—C6 | 67.77 (16) | C6—C10—H10 | 126.4 |
C5—Fe1—C6 | 166.61 (16) | Fe1—C10—H10 | 125.5 |
C3—Fe1—C6 | 120.89 (16) | C2—C21—S2 | 114.3 (2) |
C9—Fe1—C7 | 67.76 (15) | C2—C21—H21A | 108.7 |
C1—Fe1—C7 | 111.10 (13) | S2—C21—H21A | 108.7 |
C10—Fe1—C7 | 68.06 (17) | C2—C21—H21B | 108.7 |
C2—Fe1—C7 | 123.53 (13) | S2—C21—H21B | 108.7 |
C8—Fe1—C7 | 40.29 (14) | H21A—C21—H21B | 107.6 |
C5—Fe1—C7 | 128.34 (15) | C116—C111—C112 | 119.4 (3) |
C3—Fe1—C7 | 156.58 (14) | C116—C111—P1 | 121.3 (2) |
C6—Fe1—C7 | 39.94 (16) | C112—C111—P1 | 119.1 (2) |
C9—Fe1—C4 | 104.24 (15) | C113—C112—C111 | 119.9 (3) |
C1—Fe1—C4 | 68.84 (12) | C113—C112—H112 | 120.0 |
C10—Fe1—C4 | 116.42 (16) | C111—C112—H112 | 120.0 |
C2—Fe1—C4 | 68.56 (13) | C114—C113—C112 | 120.5 (3) |
C8—Fe1—C4 | 123.98 (14) | C114—C113—H113 | 119.8 |
C5—Fe1—C4 | 40.21 (14) | C112—C113—H113 | 119.8 |
C3—Fe1—C4 | 40.45 (13) | C115—C114—C113 | 119.7 (3) |
C6—Fe1—C4 | 152.99 (17) | C115—C114—H114 | 120.2 |
C7—Fe1—C4 | 162.85 (14) | C113—C114—H114 | 120.2 |
C1—P1—C121 | 105.94 (14) | C114—C115—C116 | 120.9 (3) |
C1—P1—C111 | 103.27 (14) | C114—C115—H115 | 119.6 |
C121—P1—C111 | 105.92 (14) | C116—C115—H115 | 119.6 |
C1—P1—Pd1 | 113.39 (10) | C111—C116—C115 | 119.5 (3) |
C121—P1—Pd1 | 107.77 (9) | C111—C116—H116 | 120.3 |
C111—P1—Pd1 | 119.58 (10) | C115—C116—H116 | 120.3 |
C21—S2—C211 | 98.46 (15) | C122—C121—C126 | 118.9 (3) |
C21—S2—Pd1 | 115.15 (11) | C122—C121—P1 | 122.3 (2) |
C211—S2—Pd1 | 106.66 (12) | C126—C121—P1 | 118.8 (2) |
C2—C1—C5 | 107.0 (3) | C123—C122—C121 | 120.1 (3) |
C2—C1—P1 | 124.8 (2) | C123—C122—H122 | 120.0 |
C5—C1—P1 | 128.3 (2) | C121—C122—H122 | 120.0 |
C2—C1—Fe1 | 69.40 (17) | C124—C123—C122 | 120.8 (3) |
C5—C1—Fe1 | 69.53 (17) | C124—C123—H123 | 119.6 |
P1—C1—Fe1 | 127.80 (16) | C122—C123—H123 | 119.6 |
C3—C2—C1 | 107.7 (3) | C123—C124—C125 | 120.2 (3) |
C3—C2—C21 | 127.3 (3) | C123—C124—H124 | 119.9 |
C1—C2—C21 | 124.6 (3) | C125—C124—H124 | 119.9 |
C3—C2—Fe1 | 70.14 (18) | C126—C125—C124 | 119.3 (3) |
C1—C2—Fe1 | 69.18 (16) | C126—C125—H125 | 120.3 |
C21—C2—Fe1 | 132.4 (2) | C124—C125—H125 | 120.3 |
C2—C3—C4 | 108.9 (3) | C125—C126—C121 | 120.7 (3) |
C2—C3—Fe1 | 69.36 (18) | C125—C126—H126 | 119.6 |
C4—C3—Fe1 | 69.88 (19) | C121—C126—H126 | 119.6 |
C2—C3—H3 | 125.6 | C212—C211—S2 | 115.9 (2) |
C4—C3—H3 | 125.6 | C212—C211—H21C | 108.3 |
Fe1—C3—H3 | 126.8 | S2—C211—H21C | 108.3 |
C5—C4—C3 | 108.4 (3) | C212—C211—H21D | 108.3 |
C5—C4—Fe1 | 69.59 (19) | S2—C211—H21D | 108.3 |
C3—C4—Fe1 | 69.67 (19) | H21C—C211—H21D | 107.4 |
C5—C4—H4 | 125.8 | C211—C212—H21E | 109.5 |
C3—C4—H4 | 125.8 | C211—C212—H21F | 109.5 |
Fe1—C4—H4 | 126.5 | H21E—C212—H21F | 109.5 |
C4—C5—C1 | 108.1 (3) | C211—C212—H21G | 109.5 |
C4—C5—Fe1 | 70.20 (19) | H21E—C212—H21G | 109.5 |
C1—C5—Fe1 | 68.94 (17) | H21F—C212—H21G | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···Cl1i | 0.93 | 2.68 | 3.603 (3) | 174 |
C115—H115···Cl1ii | 0.93 | 2.79 | 3.704 (4) | 168 |
C125—H125···Cl1iii | 0.93 | 2.72 | 3.554 (4) | 149 |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+2, y−1/2, −z+1/2; (iii) x+1/2, −y+3/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [PdFe(C5H5)(C20H20PS)Cl2] |
Mr | 621.63 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 180 |
a, b, c (Å) | 9.7644 (7), 14.8595 (15), 16.9586 (12) |
V (Å3) | 2460.6 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.70 |
Crystal size (mm) | 0.58 × 0.31 × 0.1 |
Data collection | |
Diffractometer | Stoe IPDS diffractometer |
Absorption correction | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.565, 0.856 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24267, 4771, 4539 |
Rint | 0.045 |
(sin θ/λ)max (Å−1) | 0.616 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.059, 1.04 |
No. of reflections | 4771 |
No. of parameters | 281 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.51, −0.53 |
Absolute structure | Flack (1983), with 2048 Friedel pairs |
Absolute structure parameter | −0.008 (17) |
Computer programs: IPDS Software (Stoe & Cie, 2000), X-RED (Stoe & Cie, 1996), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
(II) n = 1, R = C2H5 (Malacea et al., 2007). (III) n = 1, R = C6H5 (Malacea et al., 2007). (IV) n = 1, R = C(CH3)3 (Malacea et al., 2007). (V) n = 0, R = C(CH3)3 (García Mancheño et al., 2005). Cg1 and Cg2 are the centroids of the Cp rings. δ is the twist angle between the two Cp rings. |
Parameter | (I) | (II) | (III) | (IV) | (V) |
Space group | P212121 | Cc | P21/c | P21/c | P212121 |
Pd1—P1 | 2.2302 (7) | 2.2253 (16) | 2.2311 (10) | 2.2251 (8) | 2.2427 (9) |
Pd1—S2 | 2.2962 (8) | 2.3078 (18) | 2.3074 (9) | 2.3215 (8) | 2.3137 (9) |
Pd1—Cl2 | 2.2971 (8) | 2.3139 (18) | 2.3102 (9) | 2.3006 (8) | 2.3022 (11) |
Pd1—Cl1 | 2.3708 (7) | 2.3621 (17) | 2.3683 (10) | 2.3588 (8) | 2.3461 (11) |
P1—Pd1—S2 | 94.72 (3) | 93.93 (6) | 95.08 (4) | 96.08 (3) | 90.83 (3) |
P1—Pd1—Cl2 | 89.96 (3) | 89.78 (6) | 90.20 (3) | 88.99 (3) | 88.26 (4) |
P1—Pd1—Cl1 | 174.74 (3) | 176.50 (7) | 175.56 (3) | 163.68 (3) | 176.95 (4) |
S2—Pd1—Cl1 | 83.71 (3) | 83.73 (6) | 83.41 (3) | 86.73 (3) | 89.39 (4) |
S2—Pd1—Cl2 | 174.47 (3) | 176.28 (6) | 173.14 (3) | 169.98 (3) | 176.23 (4) |
Cl1—Pd1—Cl2 | 91.89 (3) | 92.55 (7) | 91.65 (4) | 90.82 (3) | 91.72 (5) |
Fe1—Cg1 | 1.6463 (4) | 1.643 (7) | 1.6523 (6) | 1.6581 (4) | |
Fe1—Cg2 | 1.6539 (4) | 1.662 (6) | 1.6651 (6) | 1.6657 (4) | |
Cg1—Fe1—Cg2 | 176.03 (7) | 174.8 (11) | 175.67 (3) | 176.96 (3) | |
δ | 8.4 (3) | 5.6 (5) | 6.8 (3) | 11.8 (2) |
D—H | H···A | D···A | D—H···A | Symmetry code | ||
Compound (I) | C4—H4···Cl1 | 0.93 | 2.68 | 3.603 (3) | 174.0 | 1-x, -1/2+y, 1/2-z |
C115—H115···Cl1 | 0.93 | 2.79 | 3.704 (4) | 168.2 | 2-x, -1/2+y, 1/2-z | |
C125—H125···Cl1 | 0.93 | 2.72 | 3.554 (4) | 149.0 | 1/2+x, 3/2-y, 1-z | |
Compound (II) | C113—H113···Cl1 | 0.95 | 2.78 | 3.474 (8) | 131.0 | x, 1-y, 1/2-z |
C114—H114···Cl1 | 0.95 | 2.82 | 3.499 (7) | 129.2 | x, y, -1+z | |
C123—H123···Cl1 | 0.95 | 2.69 | 3.560 (9) | 152.2 | -1/2+x, 1/2-y, -1/2+z |
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Owing to the huge importance of asymmetric catalysis for academic and industrial research, considerable efforts have been devoted to the development of new chiral ligands for transition metal-catalysed asymmetric catalysis (Noyori, 1994; Jacobsen et al., 1999; Ojima 2000). Chiral ferrocene-based ligands have proved to be of particular interest (Colacot, 2003; Atkinson et al., 2004; Gomez Arrayas et al., 2006) because of their stability, easy introduction of planar chirality (Togni, 1996; Riant & Kagan, 1997; Balavoine et al., 1998; Richards & Locke, 1998) and special stereoelectronic properties of the ferrocene skeleton.
We have recently developed new chiral ferrocene-based phosphine-thioether ligands having only planar chirality, in both racemic and enantiomerically pure forms (R or S configuration) (Routaboul et al., 2005; Mateus et al., 2006) and briefly reported on their coordination chemistry (Malacea, Manoury et al., 2006; Malacea, Daran et al., 2006; Malacea et al., 2007). These ligands, in enantiomerically pure forms, have been successfully applied to some asymmetric catalytic reactions, namely palladium-catalysed allylic substitution (Routaboul et al., 2005, 2007) and iridium-catalysed ketone hydrogenation (Le Roux et al., 2007).
The reaction of the planar chiral ligand (S)-2 with one equivalent of dichloridobis(acetonitrile)palladium (see scheme) quantitatively yields the title square-planar mononuclear palladium complex, (I), as a single diastereoisomer, as shown by NMR data (1H, 31P, 13C).
Compound (I) adopts a mononuclear square-planar geometry, with the phosphine and thioether functions in relative cis positions. The largest deviation from the square plane is -0.0857 (4) for atom Cl1. This plane makes a dihedral angle of 37.08 (7)° with the plane containing the substituted Cp ring and atoms P1 and C21. As observed in the racemic compound and in related Pd complexes (Malacea et al., 2007), the S substituent is located on the opposite side (anti) of the S–C–C–C–P chelate, relative to the FeCp group. Thus, the metal [Pd?] atom has been selectively coordinated by one of the two lone pairs of the S atom; after coordination, the remaining lone pair is oriented syn to the unsubstituted Cp ring. Owing to the synthetic pathway, compound (I) is an enantiomerically pure single diastereoisomer with the configuration for planar chirality being (S), and the configuration of the S atom being (R). This stereochemistry has been unequivocally determined by the structural analysis, with a value of 0.01 (2) for the enantiopole parameter (Flack, 1983). The planar chirality of the ligand is then retained in the complex and fully controls the central chirality on the S atom.
As shown in Table 1, there are no significant differences in the relevant structural parameters between compound (I) and its racemic equivalent (II) (Table 1). Although their crystal systems are different, orthorhombic for (I) and monoclinic for (II) (Table 1), their packings are roughly similar, with four molecules within the unit cell (Figs. 2 and 3) and weak C—H···Cl interactions (Steiner, 1998) (Table 2). It may be noted that only atom Cl1 is involved in these hydrogen bonds in both compounds, which reflects the electronic trans effect of the P atom.
When comparing the structure of the title compound with related structures (Malacea et al., 2007; García Mancheño et al., 2005) (Table 1), it can indeed be noted that the Pd—S bond is longer than the Pd—P bond, and the Pd—Cl bond trans to P is longer than the Pd—Cl bond trans to S, in agreement with the stronger trans effect of phosphine donors compared with thioethers (Table 1). The Pd—P distances are within the previously established range (2.228–2.237 Å) for relevant compounds found in the Cambridge Structural Database (CSD, Version 5.28; Allen, 2002), whereas the Pd—S distances are slightly longer with respect to the reported range of 2.257–2.296 Å. In compounds (I), (II), (III) and (IV), the P—Pd—S, P—Pd—Cl and S—Pd—Cl angles (Table 1) seem to be influenced by the growing steric repulsion between the S substituent and the pseudo-axial phosphine Ph group. Indeed, the largest differences are observed for compound (IV), where the S atom bears a bulky tBu substituent. In compound (V), where the S atom is directly bonded to the Cp ring (García Mancheño et al., 2005), the square-planar framework is nearly perfect, with all angles close to 90 or 180°.