![](/logos/buttonlogos/cross.png)
![](/logos/buttonlogos/cross.png)
metal-organic compounds
1,1′-Bis[bis(4-methoxyphenyl)phosphanyl]ferrocene
aCollege of Chemistry and Chemical Engineering, Shanghai University of Engineering Science, Shanghai 201620, People's Republic of China
*Correspondence e-mail: renxf@sues.edu.cn
In the 19H18O2P)2], the FeII atom lies on a twofold rotation axis, giving an eclipsed cyclopentadienyl conformation with a ring centroid separation of 3.292 (7) Å and an Fe—C bond-length range of 2.0239 (15)–2.0521 (15) Å. In the ligand, the cyclopentadienyl ring forms dihedral angles of 60.36 (6) and 82.93 (6)° with the two benzene rings of the diphenylphosphine group, while the dihedral angle between the benzene rings is 67.4 (5)°.
of the title substituted ferrocene complex, [Fe(CRelated literature
For the synthesis of the title compound from ferrocene, see: Ogasawara et al. (2002). For applications of the title compound, see: Gusev et al. (2006
); Hamann & Hartwig (1998
); Casellato et al. (1988
).
Experimental
Crystal data
|
Data collection: SMART (Bruker, 2007); cell SAINT (Bruker, 2007
); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008
); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008
); molecular graphics: SHELXTL (Sheldrick, 2008
); software used to prepare material for publication: SHELXTL.
Supporting information
https://doi.org/10.1107/S1600536812026293/zs2202sup1.cif
contains datablocks I, global. DOI:Supporting information file. DOI: https://doi.org/10.1107/S1600536812026293/zs2202Isup2.cdx
Supporting information file. DOI: https://doi.org/10.1107/S1600536812026293/zs2202Isup4.cdx
Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812026293/zs2202Isup3.hkl
A solution of 4-methoxyphenylmagnesium bromide (1 M in THF, 12 ml, 12 mmol) was added dropwise over 5 min. at -78 °C to a stirred solution of 1,1'-bis(dichlorophosphanyl)ferrocene (776 mg, 2 mmol) in THF (15 ml) under argon. The mixture was warmed to 25 °C slowly and was stirred for an additional 12 h. The reaction was monitored by PNMR. The resulting mixture was quenched with water (2 ml) at 0 °C, and then filtered and washed with water (10×, 3 ml), methanol (5×, 2 ml) and diethyl ether (5×, 3 ml). The solid obtained was then dissolved in chloroform (5 ml) and the solution was passed through a short silica gel plug, and washed with chloroform (5×, 3 ml) to remove the residual salt. The solvent was removed and the resulting solid was dried under vacuum to give the title compound as a yellow solid (680 mg, 50.5% yield). Single crystals suitable for X-ray diffraction are obtained from a CH2Cl2-hexane solution via solvent evaporation at room temperature after two weeks.
All H-atoms were placed in calculated positions with C—H = 0.93 Å and were allowed to ride in the
with U</>iso(H) = 1.2Ueq(C).The title compound is a substituted ferrocene complex [C38H36FeO4P2] which was synthesized in a reaction of 4-methoxyphenylmagnesium bromide with 1,1'-bis(dichlorophosphine)ferrocene. A previously reported synthesis involved the reaction of chlorobis(4-methoxyphenyl)phosphine with ferrocene (Ogasawara et al., 2002). A potential application of the compound is in metal-catalized organic reactions (Gusev et al., 2006; Hamann & Hartwig, 1998). The single-crystal
of the compound was performed to provide the coordination geometry and structural conformation, which will allow the study of the mechanism of metal-catalized organic reactions.In the structure of the title compound, the FeII lies on a twofold rotation axis giving an eclipsed cyclopentadienyl configuration (Fig. 1), with a cyclopentadienyl ring-centroid separation of 3.292 (7) Å and an Fe—C range of 2.0239 (15)–2.0521 (15) Å. These distances compare with 3.305 (3) and 2.033 (4)–2.064 (4) Å in a similar ferrocene complex (Casellato et al., 1988). In each ligand, the cyclopentadienyl ring forms dihedral angles of 60.36 (6)° and 82.93 (6)° with the two phenyl rings of the diphenylphosphine substituent group, while the dihedral angle between the phenyl rings is 67.4 (5)°.
For the synthesis of the title compound from ferrocene, see: Ogasawara et al. (2002). For applications of the title compound, see: Gusev et al. (2006); Hamann & Hartwig (1998); Casellato et al. (1988).
Data collection: SMART (Bruker, 2007); cell
SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008). ![]() | Fig. 1. Molecular configuration and atom-numbering scheme for the title compound, with probability displacement ellipsoids drawn at the 50% level. For symmetry code (i): -x, y, -z+1/2. |
[Fe(C19H18O2P)2] | F(000) = 1408 |
Mr = 674.46 | Dx = 1.376 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 9910 reflections |
a = 19.0790 (8) Å | θ = 2.3–28.3° |
b = 9.9445 (4) Å | µ = 0.60 mm−1 |
c = 17.5663 (8) Å | T = 173 K |
β = 102.386 (1)° | Block, yellow |
V = 3255.3 (2) Å3 | 0.48 × 0.46 × 0.32 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 2869 independent reflections |
Radiation source: fine-focus sealed tube | 2740 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
φ and ω scans | θmax = 25.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −22→22 |
Tmin = 0.761, Tmax = 0.831 | k = −11→11 |
18254 measured reflections | l = −20→20 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.026 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.070 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0343P)2 + 3.7311P] where P = (Fo2 + 2Fc2)/3 |
2869 reflections | (Δ/σ)max < 0.001 |
204 parameters | Δρmax = 0.34 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
[Fe(C19H18O2P)2] | V = 3255.3 (2) Å3 |
Mr = 674.46 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 19.0790 (8) Å | µ = 0.60 mm−1 |
b = 9.9445 (4) Å | T = 173 K |
c = 17.5663 (8) Å | 0.48 × 0.46 × 0.32 mm |
β = 102.386 (1)° |
Bruker SMART CCD area-detector diffractometer | 2869 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2740 reflections with I > 2σ(I) |
Tmin = 0.761, Tmax = 0.831 | Rint = 0.019 |
18254 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.070 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.34 e Å−3 |
2869 reflections | Δρmin = −0.18 e Å−3 |
204 parameters |
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 | ||
Fe1 | 0.0000 | 0.11062 (3) | 0.2500 | 0.02319 (10) | |
P1 | 0.11216 (2) | 0.17867 (4) | 0.12853 (2) | 0.02453 (11) | |
O1 | 0.06477 (7) | 0.44156 (13) | −0.18422 (7) | 0.0424 (3) | |
O2 | 0.22904 (6) | −0.37992 (11) | 0.13592 (7) | 0.0382 (3) | |
C1 | 0.09423 (8) | 0.23741 (15) | 0.02723 (9) | 0.0248 (3) | |
C2 | 0.03081 (9) | 0.30448 (18) | −0.00579 (10) | 0.0366 (4) | |
H2A | −0.0076 | 0.3054 | 0.0209 | 0.044* | |
C3 | 0.02282 (10) | 0.3694 (2) | −0.07642 (11) | 0.0414 (4) | |
H3A | −0.0210 | 0.4140 | −0.0979 | 0.050* | |
C4 | 0.07794 (9) | 0.37024 (16) | −0.11638 (9) | 0.0302 (3) | |
C5 | 0.14120 (8) | 0.30234 (16) | −0.08555 (9) | 0.0298 (3) | |
H5A | 0.1791 | 0.3003 | −0.1129 | 0.036* | |
C6 | 0.14846 (8) | 0.23725 (16) | −0.01420 (9) | 0.0287 (3) | |
H6A | 0.1919 | 0.1912 | 0.0068 | 0.034* | |
C7 | 0.14856 (8) | 0.00986 (15) | 0.12251 (9) | 0.0250 (3) | |
C8 | 0.19314 (8) | −0.04129 (16) | 0.18999 (9) | 0.0280 (3) | |
H8A | 0.2058 | 0.0142 | 0.2349 | 0.034* | |
C9 | 0.21914 (8) | −0.17124 (16) | 0.19252 (9) | 0.0312 (3) | |
H9A | 0.2488 | −0.2049 | 0.2390 | 0.037* | |
C10 | 0.20173 (8) | −0.25261 (15) | 0.12684 (9) | 0.0281 (3) | |
C11 | 0.15920 (8) | −0.20285 (16) | 0.05856 (9) | 0.0298 (3) | |
H11A | 0.1484 | −0.2574 | 0.0131 | 0.036* | |
C12 | 0.13253 (8) | −0.07256 (16) | 0.05713 (9) | 0.0292 (3) | |
H12A | 0.1028 | −0.0392 | 0.0106 | 0.035* | |
C13 | −0.08978 (9) | 0.16360 (19) | 0.16939 (9) | 0.0356 (4) | |
H13A | −0.1341 | 0.2053 | 0.1808 | 0.043* | |
C14 | −0.02860 (9) | 0.23385 (17) | 0.15681 (9) | 0.0311 (3) | |
H14A | −0.0226 | 0.3338 | 0.1572 | 0.037* | |
C15 | 0.02275 (8) | 0.13737 (16) | 0.14232 (8) | 0.0261 (3) | |
C16 | −0.00775 (9) | 0.00717 (17) | 0.14745 (9) | 0.0314 (3) | |
H16A | 0.0158 | −0.0808 | 0.1411 | 0.038* | |
C17 | −0.07674 (9) | 0.02422 (19) | 0.16437 (9) | 0.0370 (4) | |
H17A | −0.1102 | −0.0497 | 0.1719 | 0.044* | |
C18 | 0.21229 (11) | −0.46909 (18) | 0.07098 (12) | 0.0456 (4) | |
H18A | 0.2351 | −0.5564 | 0.0854 | 0.068* | |
H18B | 0.2301 | −0.4313 | 0.0272 | 0.068* | |
H18C | 0.1602 | −0.4809 | 0.0557 | 0.068* | |
C19 | 0.11777 (11) | 0.4448 (3) | −0.22871 (12) | 0.0557 (6) | |
H19A | 0.1009 | 0.4995 | −0.2755 | 0.084* | |
H19B | 0.1275 | 0.3531 | −0.2440 | 0.084* | |
H19C | 0.1618 | 0.4842 | −0.1977 | 0.084* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.02589 (17) | 0.02243 (17) | 0.02163 (17) | 0.000 | 0.00595 (12) | 0.000 |
P1 | 0.0268 (2) | 0.0228 (2) | 0.0238 (2) | −0.00004 (14) | 0.00500 (15) | −0.00076 (15) |
O1 | 0.0477 (7) | 0.0485 (7) | 0.0333 (6) | 0.0126 (6) | 0.0140 (5) | 0.0159 (6) |
O2 | 0.0407 (7) | 0.0262 (6) | 0.0440 (7) | 0.0073 (5) | 0.0007 (5) | −0.0013 (5) |
C1 | 0.0274 (7) | 0.0213 (7) | 0.0253 (7) | −0.0014 (6) | 0.0047 (6) | −0.0006 (6) |
C2 | 0.0303 (8) | 0.0469 (10) | 0.0350 (9) | 0.0070 (7) | 0.0121 (7) | 0.0097 (8) |
C3 | 0.0320 (9) | 0.0526 (11) | 0.0402 (10) | 0.0145 (8) | 0.0095 (7) | 0.0140 (8) |
C4 | 0.0368 (9) | 0.0263 (8) | 0.0276 (8) | 0.0014 (6) | 0.0070 (7) | 0.0026 (6) |
C5 | 0.0307 (8) | 0.0305 (8) | 0.0303 (8) | 0.0006 (6) | 0.0114 (6) | −0.0001 (7) |
C6 | 0.0277 (7) | 0.0276 (8) | 0.0305 (8) | 0.0039 (6) | 0.0057 (6) | 0.0016 (6) |
C7 | 0.0237 (7) | 0.0251 (7) | 0.0263 (7) | −0.0001 (6) | 0.0058 (6) | 0.0008 (6) |
C8 | 0.0271 (7) | 0.0301 (8) | 0.0255 (7) | −0.0009 (6) | 0.0025 (6) | −0.0027 (6) |
C9 | 0.0292 (8) | 0.0326 (9) | 0.0290 (8) | 0.0029 (6) | −0.0005 (6) | 0.0043 (7) |
C10 | 0.0245 (7) | 0.0245 (7) | 0.0357 (8) | 0.0005 (6) | 0.0075 (6) | 0.0019 (6) |
C11 | 0.0326 (8) | 0.0289 (8) | 0.0275 (8) | −0.0006 (6) | 0.0050 (6) | −0.0041 (6) |
C12 | 0.0321 (8) | 0.0296 (8) | 0.0238 (8) | 0.0030 (7) | 0.0014 (6) | 0.0020 (6) |
C13 | 0.0272 (8) | 0.0549 (11) | 0.0240 (8) | 0.0054 (7) | 0.0041 (6) | 0.0032 (7) |
C14 | 0.0344 (8) | 0.0340 (9) | 0.0254 (8) | 0.0081 (7) | 0.0075 (6) | 0.0064 (7) |
C15 | 0.0298 (8) | 0.0285 (8) | 0.0203 (7) | 0.0008 (6) | 0.0058 (6) | 0.0008 (6) |
C16 | 0.0371 (9) | 0.0317 (8) | 0.0261 (8) | −0.0071 (7) | 0.0085 (7) | −0.0071 (6) |
C17 | 0.0341 (9) | 0.0498 (10) | 0.0270 (8) | −0.0136 (8) | 0.0068 (7) | −0.0084 (7) |
C18 | 0.0499 (11) | 0.0287 (9) | 0.0560 (12) | 0.0055 (8) | 0.0067 (9) | −0.0084 (8) |
C19 | 0.0541 (12) | 0.0745 (15) | 0.0435 (11) | 0.0102 (11) | 0.0215 (9) | 0.0259 (11) |
Fe1—C14 | 2.0239 (15) | C6—H6A | 0.9500 |
Fe1—C14i | 2.0239 (15) | C7—C12 | 1.390 (2) |
Fe1—C13i | 2.0436 (16) | C7—C8 | 1.398 (2) |
Fe1—C13 | 2.0437 (16) | C8—C9 | 1.381 (2) |
Fe1—C15 | 2.0467 (14) | C8—H8A | 0.9500 |
Fe1—C15i | 2.0468 (14) | C9—C10 | 1.390 (2) |
Fe1—C17 | 2.0493 (16) | C9—H9A | 0.9500 |
Fe1—C17i | 2.0493 (16) | C10—C11 | 1.387 (2) |
Fe1—C16i | 2.0521 (15) | C11—C12 | 1.390 (2) |
Fe1—C16 | 2.0521 (15) | C11—H11A | 0.9500 |
P1—C15 | 1.8207 (16) | C12—H12A | 0.9500 |
P1—C7 | 1.8284 (15) | C13—C17 | 1.414 (3) |
P1—C1 | 1.8341 (15) | C13—C14 | 1.418 (2) |
O1—C4 | 1.3630 (19) | C13—H13A | 1.0000 |
O1—C19 | 1.405 (2) | C14—C15 | 1.432 (2) |
O2—C10 | 1.3653 (19) | C14—H14A | 1.0000 |
O2—C18 | 1.426 (2) | C15—C16 | 1.430 (2) |
C1—C6 | 1.387 (2) | C16—C17 | 1.420 (2) |
C1—C2 | 1.394 (2) | C16—H16A | 1.0000 |
C2—C3 | 1.378 (2) | C17—H17A | 1.0000 |
C2—H2A | 0.9500 | C18—H18A | 0.9800 |
C3—C4 | 1.384 (2) | C18—H18B | 0.9800 |
C3—H3A | 0.9500 | C18—H18C | 0.9800 |
C4—C5 | 1.388 (2) | C19—H19A | 0.9800 |
C5—C6 | 1.391 (2) | C19—H19B | 0.9800 |
C5—H5A | 0.9500 | C19—H19C | 0.9800 |
C14—Fe1—C14i | 105.47 (10) | C6—C5—H5A | 120.4 |
C14—Fe1—C13i | 116.41 (7) | C1—C6—C5 | 122.08 (14) |
C14i—Fe1—C13i | 40.79 (7) | C1—C6—H6A | 119.0 |
C14—Fe1—C13 | 40.80 (7) | C5—C6—H6A | 119.0 |
C14i—Fe1—C13 | 116.41 (7) | C12—C7—C8 | 118.15 (14) |
C13i—Fe1—C13 | 150.12 (11) | C12—C7—P1 | 124.75 (12) |
C14—Fe1—C15 | 41.20 (6) | C8—C7—P1 | 117.03 (11) |
C14i—Fe1—C15 | 126.51 (6) | C9—C8—C7 | 121.10 (14) |
C13i—Fe1—C15 | 107.13 (6) | C9—C8—H8A | 119.5 |
C13—Fe1—C15 | 68.81 (6) | C7—C8—H8A | 119.5 |
C14—Fe1—C15i | 126.51 (6) | C8—C9—C10 | 119.85 (14) |
C14i—Fe1—C15i | 41.20 (6) | C8—C9—H9A | 120.1 |
C13i—Fe1—C15i | 68.81 (6) | C10—C9—H9A | 120.1 |
C13—Fe1—C15i | 107.13 (6) | O2—C10—C11 | 124.73 (14) |
C15—Fe1—C15i | 165.06 (9) | O2—C10—C9 | 115.18 (14) |
C14—Fe1—C17 | 68.53 (7) | C11—C10—C9 | 120.09 (14) |
C14i—Fe1—C17 | 150.90 (7) | C10—C11—C12 | 119.47 (14) |
C13i—Fe1—C17 | 167.79 (8) | C10—C11—H11A | 120.3 |
C13—Fe1—C17 | 40.43 (8) | C12—C11—H11A | 120.3 |
C15—Fe1—C17 | 68.65 (6) | C11—C12—C7 | 121.31 (14) |
C15i—Fe1—C17 | 118.24 (6) | C11—C12—H12A | 119.3 |
C14—Fe1—C17i | 150.90 (7) | C7—C12—H12A | 119.3 |
C14i—Fe1—C17i | 68.53 (7) | C17—C13—C14 | 108.14 (15) |
C13i—Fe1—C17i | 40.43 (8) | C17—C13—Fe1 | 70.00 (10) |
C13—Fe1—C17i | 167.79 (8) | C14—C13—Fe1 | 68.85 (9) |
C15—Fe1—C17i | 118.24 (6) | C17—C13—H13A | 125.9 |
C15i—Fe1—C17i | 68.64 (6) | C14—C13—H13A | 125.9 |
C17—Fe1—C17i | 130.42 (11) | Fe1—C13—H13A | 125.9 |
C14—Fe1—C16i | 165.87 (6) | C13—C14—C15 | 108.36 (15) |
C14i—Fe1—C16i | 68.74 (7) | C13—C14—Fe1 | 70.35 (9) |
C13i—Fe1—C16i | 68.23 (7) | C15—C14—Fe1 | 70.25 (9) |
C13—Fe1—C16i | 129.00 (7) | C13—C14—H14A | 125.8 |
C15—Fe1—C16i | 152.47 (6) | C15—C14—H14A | 125.8 |
C15i—Fe1—C16i | 40.85 (6) | Fe1—C14—H14A | 125.8 |
C17—Fe1—C16i | 109.86 (7) | C16—C15—C14 | 106.99 (14) |
C17i—Fe1—C16i | 40.52 (7) | C16—C15—P1 | 128.17 (12) |
C14—Fe1—C16 | 68.74 (7) | C14—C15—P1 | 124.65 (12) |
C14i—Fe1—C16 | 165.87 (6) | C16—C15—Fe1 | 69.78 (8) |
C13i—Fe1—C16 | 129.01 (7) | C14—C15—Fe1 | 68.54 (8) |
C13—Fe1—C16 | 68.23 (7) | P1—C15—Fe1 | 122.87 (8) |
C15—Fe1—C16 | 40.85 (6) | C17—C16—C15 | 108.23 (15) |
C15i—Fe1—C16 | 152.47 (6) | C17—C16—Fe1 | 69.63 (9) |
C17—Fe1—C16 | 40.52 (7) | C15—C16—Fe1 | 69.37 (8) |
C17i—Fe1—C16 | 109.86 (7) | C17—C16—H16A | 125.9 |
C16i—Fe1—C16 | 119.82 (9) | C15—C16—H16A | 125.9 |
C15—P1—C7 | 100.31 (7) | Fe1—C16—H16A | 125.9 |
C15—P1—C1 | 102.46 (7) | C13—C17—C16 | 108.27 (15) |
C7—P1—C1 | 103.32 (7) | C13—C17—Fe1 | 69.57 (9) |
C4—O1—C19 | 118.61 (14) | C16—C17—Fe1 | 69.85 (9) |
C10—O2—C18 | 117.95 (13) | C13—C17—H17A | 125.9 |
C6—C1—C2 | 117.43 (14) | C16—C17—H17A | 125.9 |
C6—C1—P1 | 120.27 (11) | Fe1—C17—H17A | 125.9 |
C2—C1—P1 | 121.37 (12) | O2—C18—H18A | 109.5 |
C3—C2—C1 | 121.15 (15) | O2—C18—H18B | 109.5 |
C3—C2—H2A | 119.4 | H18A—C18—H18B | 109.5 |
C1—C2—H2A | 119.4 | O2—C18—H18C | 109.5 |
C2—C3—C4 | 120.68 (16) | H18A—C18—H18C | 109.5 |
C2—C3—H3A | 119.7 | H18B—C18—H18C | 109.5 |
C4—C3—H3A | 119.7 | O1—C19—H19A | 109.5 |
O1—C4—C3 | 115.40 (15) | O1—C19—H19B | 109.5 |
O1—C4—C5 | 125.18 (15) | H19A—C19—H19B | 109.5 |
C3—C4—C5 | 119.41 (15) | O1—C19—H19C | 109.5 |
C4—C5—C6 | 119.23 (14) | H19A—C19—H19C | 109.5 |
C4—C5—H5A | 120.4 | H19B—C19—H19C | 109.5 |
C15—P1—C1—C6 | −158.86 (12) | C1—P1—C15—C16 | 106.83 (14) |
C7—P1—C1—C6 | −54.93 (14) | C7—P1—C15—C14 | 174.94 (13) |
C15—P1—C1—C2 | 32.47 (15) | C1—P1—C15—C14 | −78.80 (14) |
C7—P1—C1—C2 | 136.39 (14) | C7—P1—C15—Fe1 | 89.69 (10) |
C6—C1—C2—C3 | −0.8 (3) | C1—P1—C15—Fe1 | −164.05 (9) |
P1—C1—C2—C3 | 168.20 (15) | C14—Fe1—C15—C16 | −118.64 (13) |
C1—C2—C3—C4 | −0.3 (3) | C14i—Fe1—C15—C16 | 171.34 (10) |
C19—O1—C4—C3 | −178.81 (19) | C13i—Fe1—C15—C16 | 130.58 (10) |
C19—O1—C4—C5 | 2.0 (3) | C13—Fe1—C15—C16 | −80.81 (10) |
C2—C3—C4—O1 | −177.80 (17) | C15i—Fe1—C15—C16 | −157.63 (9) |
C2—C3—C4—C5 | 1.4 (3) | C17—Fe1—C15—C16 | −37.27 (10) |
O1—C4—C5—C6 | 177.74 (15) | C17i—Fe1—C15—C16 | 88.20 (11) |
C3—C4—C5—C6 | −1.4 (2) | C16i—Fe1—C15—C16 | 55.0 (2) |
C2—C1—C6—C5 | 0.8 (2) | C14i—Fe1—C15—C14 | −70.02 (15) |
P1—C1—C6—C5 | −168.32 (12) | C13i—Fe1—C15—C14 | −110.77 (10) |
C4—C5—C6—C1 | 0.3 (2) | C13—Fe1—C15—C14 | 37.84 (10) |
C15—P1—C7—C12 | 77.75 (14) | C15i—Fe1—C15—C14 | −38.99 (9) |
C1—P1—C7—C12 | −27.83 (15) | C17—Fe1—C15—C14 | 81.37 (11) |
C15—P1—C7—C8 | −99.24 (12) | C17i—Fe1—C15—C14 | −153.16 (10) |
C1—P1—C7—C8 | 155.18 (12) | C16i—Fe1—C15—C14 | 173.61 (13) |
C12—C7—C8—C9 | −1.7 (2) | C16—Fe1—C15—C14 | 118.64 (13) |
P1—C7—C8—C9 | 175.54 (12) | C14—Fe1—C15—P1 | 118.25 (14) |
C7—C8—C9—C10 | 0.9 (2) | C14i—Fe1—C15—P1 | 48.23 (13) |
C18—O2—C10—C11 | −0.6 (2) | C13i—Fe1—C15—P1 | 7.48 (12) |
C18—O2—C10—C9 | 179.14 (15) | C13—Fe1—C15—P1 | 156.09 (12) |
C8—C9—C10—O2 | −178.84 (14) | C15i—Fe1—C15—P1 | 79.27 (9) |
C8—C9—C10—C11 | 0.9 (2) | C17—Fe1—C15—P1 | −160.38 (12) |
O2—C10—C11—C12 | 177.88 (14) | C17i—Fe1—C15—P1 | −34.91 (12) |
C9—C10—C11—C12 | −1.9 (2) | C16i—Fe1—C15—P1 | −68.14 (18) |
C10—C11—C12—C7 | 1.1 (2) | C16—Fe1—C15—P1 | −123.11 (14) |
C8—C7—C12—C11 | 0.7 (2) | C14—C15—C16—C17 | 0.31 (18) |
P1—C7—C12—C11 | −176.27 (12) | P1—C15—C16—C17 | 175.46 (12) |
C14—Fe1—C13—C17 | 119.74 (14) | Fe1—C15—C16—C17 | 58.97 (11) |
C14i—Fe1—C13—C17 | −157.13 (9) | C14—C15—C16—Fe1 | −58.66 (10) |
C13i—Fe1—C13—C17 | 169.20 (10) | P1—C15—C16—Fe1 | 116.49 (12) |
C15—Fe1—C13—C17 | 81.54 (10) | C14—Fe1—C16—C17 | −81.42 (11) |
C15i—Fe1—C13—C17 | −113.69 (10) | C14i—Fe1—C16—C17 | −149.5 (3) |
C17i—Fe1—C13—C17 | −45.9 (4) | C13i—Fe1—C16—C17 | 171.18 (11) |
C16i—Fe1—C13—C17 | −73.95 (12) | C13—Fe1—C16—C17 | −37.41 (11) |
C16—Fe1—C13—C17 | 37.49 (10) | C15—Fe1—C16—C17 | −119.76 (14) |
C14i—Fe1—C13—C14 | 83.13 (13) | C15i—Fe1—C16—C17 | 47.99 (19) |
C13i—Fe1—C13—C14 | 49.46 (9) | C17i—Fe1—C16—C17 | 129.68 (13) |
C15—Fe1—C13—C14 | −38.20 (9) | C16i—Fe1—C16—C17 | 86.11 (10) |
C15i—Fe1—C13—C14 | 126.58 (10) | C14—Fe1—C16—C15 | 38.34 (9) |
C17—Fe1—C13—C14 | −119.74 (14) | C14i—Fe1—C16—C15 | −29.7 (3) |
C17i—Fe1—C13—C14 | −165.6 (3) | C13i—Fe1—C16—C15 | −69.06 (12) |
C16i—Fe1—C13—C14 | 166.31 (10) | C13—Fe1—C16—C15 | 82.34 (10) |
C16—Fe1—C13—C14 | −82.24 (10) | C15i—Fe1—C16—C15 | 167.75 (9) |
C17—C13—C14—C15 | 1.07 (18) | C17—Fe1—C16—C15 | 119.76 (14) |
Fe1—C13—C14—C15 | 60.23 (10) | C17i—Fe1—C16—C15 | −110.57 (10) |
C17—C13—C14—Fe1 | −59.16 (11) | C16i—Fe1—C16—C15 | −154.14 (10) |
C14i—Fe1—C14—C13 | −112.69 (11) | C14—C13—C17—C16 | −0.88 (19) |
C13i—Fe1—C14—C13 | −154.99 (10) | Fe1—C13—C17—C16 | −59.33 (11) |
C15—Fe1—C14—C13 | 118.92 (14) | C14—C13—C17—Fe1 | 58.45 (11) |
C15i—Fe1—C14—C13 | −72.72 (12) | C15—C16—C17—C13 | 0.34 (19) |
C17—Fe1—C14—C13 | 37.24 (10) | Fe1—C16—C17—C13 | 59.15 (11) |
C17i—Fe1—C14—C13 | 173.79 (14) | C15—C16—C17—Fe1 | −58.81 (11) |
C16i—Fe1—C14—C13 | −48.9 (3) | C14—Fe1—C17—C13 | −37.56 (10) |
C16—Fe1—C14—C13 | 80.90 (11) | C14i—Fe1—C17—C13 | 45.70 (18) |
C14i—Fe1—C14—C15 | 128.39 (10) | C13i—Fe1—C17—C13 | −153.8 (3) |
C13i—Fe1—C14—C15 | 86.09 (11) | C15—Fe1—C17—C13 | −81.98 (10) |
C13—Fe1—C14—C15 | −118.92 (14) | C15i—Fe1—C17—C13 | 83.40 (11) |
C15i—Fe1—C14—C15 | 168.36 (7) | C17i—Fe1—C17—C13 | 168.49 (10) |
C17—Fe1—C14—C15 | −81.68 (10) | C16i—Fe1—C17—C13 | 127.43 (10) |
C17i—Fe1—C14—C15 | 54.88 (18) | C16—Fe1—C17—C13 | −119.54 (14) |
C16i—Fe1—C14—C15 | −167.8 (3) | C14—Fe1—C17—C16 | 81.98 (11) |
C16—Fe1—C14—C15 | −38.02 (9) | C14i—Fe1—C17—C16 | 165.24 (13) |
C13—C14—C15—C16 | −0.85 (17) | C13i—Fe1—C17—C16 | −34.3 (4) |
Fe1—C14—C15—C16 | 59.44 (10) | C13—Fe1—C17—C16 | 119.54 (14) |
C13—C14—C15—P1 | −176.22 (11) | C15—Fe1—C17—C16 | 37.56 (10) |
Fe1—C14—C15—P1 | −115.93 (11) | C15i—Fe1—C17—C16 | −157.06 (10) |
C13—C14—C15—Fe1 | −60.29 (11) | C17i—Fe1—C17—C16 | −71.97 (10) |
C7—P1—C15—C16 | 0.58 (15) | C16i—Fe1—C17—C16 | −113.03 (12) |
Symmetry code: (i) −x, y, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Fe(C19H18O2P)2] |
Mr | 674.46 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 173 |
a, b, c (Å) | 19.0790 (8), 9.9445 (4), 17.5663 (8) |
β (°) | 102.386 (1) |
V (Å3) | 3255.3 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.60 |
Crystal size (mm) | 0.48 × 0.46 × 0.32 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.761, 0.831 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18254, 2869, 2740 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.070, 1.04 |
No. of reflections | 2869 |
No. of parameters | 204 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.34, −0.18 |
Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Acknowledgements
The authors acknowledge financial support by the National Natural Science Foundation of China (21102089), the Research Innovation Program of Shanghai Municipal Education Commission (12YZ155), the Special Scientific Foundation for Outstanding Young Teachers in Shanghai Higher Education Institutions (gjd10003, shgcjs023) and the Key Laboratory of Organofluorine Chemistry (Chinese Academy of Sciences).
References
Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Casellato, U., Ajo, D., Valle, G., Corain, B., Longato, B. & Graziani, R. (1988). J. Crystallogr. Spectrosc. Res. 18, 583–590. CSD CrossRef CAS Web of Science Google Scholar
Gusev, O. V., Peganova, T. A., Kalsin, A. M., Vologdin, N. V., Petrovskii, P. V., Lyssenko, K. A., Tsvetkov, A. V. & Beletskaya, I. P. (2006). Organometallics, 25, 2750–2760. Web of Science CSD CrossRef CAS Google Scholar
Hamann, B. C. & Hartwig, J. F. (1998). J. Am. Chem. Soc. 120, 3694–3703. Web of Science CrossRef CAS Google Scholar
Ogasawara, M., Takizawa, K. & Hayashi, T. (2002). Organometallics, 21, 4853–4861. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
The title compound is a substituted ferrocene complex [C38H36FeO4P2] which was synthesized in a reaction of 4-methoxyphenylmagnesium bromide with 1,1'-bis(dichlorophosphine)ferrocene. A previously reported synthesis involved the reaction of chlorobis(4-methoxyphenyl)phosphine with ferrocene (Ogasawara et al., 2002). A potential application of the compound is in metal-catalized organic reactions (Gusev et al., 2006; Hamann & Hartwig, 1998). The single-crystal structure determination of the compound was performed to provide the coordination geometry and structural conformation, which will allow the study of the mechanism of metal-catalized organic reactions.
In the structure of the title compound, the FeII lies on a twofold rotation axis giving an eclipsed cyclopentadienyl configuration (Fig. 1), with a cyclopentadienyl ring-centroid separation of 3.292 (7) Å and an Fe—C range of 2.0239 (15)–2.0521 (15) Å. These distances compare with 3.305 (3) and 2.033 (4)–2.064 (4) Å in a similar ferrocene complex (Casellato et al., 1988). In each ligand, the cyclopentadienyl ring forms dihedral angles of 60.36 (6)° and 82.93 (6)° with the two phenyl rings of the diphenylphosphine substituent group, while the dihedral angle between the phenyl rings is 67.4 (5)°.