Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801011448/tk6032sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801011448/tk6032Isup2.hkl |
CCDC reference: 170868
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.004 Å
- Disorder in main residue
- R factor = 0.026
- wR factor = 0.062
- Data-to-parameter ratio = 16.7
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
PLAT_301 Alert C Main Residue Disorder ........................ 12.00 Perc.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
[Rh(trop)(CO)2] (Leipoldt et al., 1980) (10 mg, 0.036 mmol) was dissolved in warm acetone (ca 4 ml, 313 K), PFcPh2 (Sollot et al., 1963) (10 mg, 0.027 mmol) was added as the solid, and the solution was filtered. Cooling to room temperature and slow evaporation of the solvent yielded crystals suitable for X-ray analysis. Yield: quantitative based on the phosphine. Spectral data, IR (KBr): ν(CO) 1965 cm-1, (CH2Cl2) ν(CO) 1974 cm-1. 1H NMR (CDCl3, 300 MHz): 4.43 (q, 4H), 4.22 (s, 5H), 7.3 (m, 15H). 31P NMR (CDCl3, 121.497 MHz): 41.21 (d), 1J(Rh—P) 174 Hz.
Some disorder was identified in the β-cyclopentadienyl ring (β1: C41A–C45A; β2: C41B—C45B). Statistical averaging and similar displacement parameters for each paired set of C atoms resolved the disorder of the system, significantly decreasing the reliability index, R, from 0.058 to 0.036. H atoms were placed in idealized positions using a riding model and thermal movement refined using an overall equivalent isotropic displacement parameter.
Data collection: SMART (Siemens, 1995); cell refinement: SMART; data reduction: SHELXTL (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97.
[Rh(C7H5O2)(C22H19FeP)(CO)] | F(000) = 1256 |
Mr = 622.22 | Dx = 1.629 Mg m−3 Dm = 1.630 Mg m−3 Dm measured by flotation in aqueous KI |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 11.3122 (7) Å | Cell parameters from 6239 reflections |
b = 16.2035 (9) Å | θ = 2.8–28.3° |
c = 14.2663 (8) Å | µ = 1.32 mm−1 |
β = 104.046 (10)° | T = 293 K |
V = 2536.8 (3) Å3 | Prism, orange |
Z = 4 | 0.30 × 0.26 × 0.20 mm |
Siemens SMART CCD 1K diffractometer | 6239 independent reflections |
Radiation source: fine-focus sealed tube | 5239 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
Detector resolution: 512 x 512 pixels mm-1 | θmax = 28.3°, θmin = 5.6° |
ω scans | h = −15→15 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −21→21 |
Tmin = 0.694, Tmax = 0.779 | l = −19→18 |
27848 measured reflections |
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: riding model |
wR(F2) = 0.062 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0258P)2 + 0.9003P] where P = (Fo2 + 2Fc2)/3 |
6239 reflections | (Δ/σ)max = 0.035 |
373 parameters | Δρmax = 0.26 e Å−3 |
42 restraints | Δρmin = −0.38 e Å−3 |
[Rh(C7H5O2)(C22H19FeP)(CO)] | V = 2536.8 (3) Å3 |
Mr = 622.22 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.3122 (7) Å | µ = 1.32 mm−1 |
b = 16.2035 (9) Å | T = 293 K |
c = 14.2663 (8) Å | 0.30 × 0.26 × 0.20 mm |
β = 104.046 (10)° |
Siemens SMART CCD 1K diffractometer | 6239 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 5239 reflections with I > 2σ(I) |
Tmin = 0.694, Tmax = 0.779 | Rint = 0.025 |
27848 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | 42 restraints |
wR(F2) = 0.062 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.26 e Å−3 |
6239 reflections | Δρmin = −0.38 e Å−3 |
373 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. Cone angles are calculated assuming a 1.2 Å radius for hydrogen atoms. |
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 | Occ. (<1) | |
Rh | 0.570333 (12) | 0.409827 (10) | 0.619893 (10) | 0.03996 (5) | |
Fe | 0.74080 (2) | 0.609115 (18) | 0.83402 (2) | 0.04377 (8) | |
P | 0.54850 (4) | 0.43830 (3) | 0.76838 (4) | 0.04003 (11) | |
O3 | 0.75679 (13) | 0.40344 (11) | 0.65573 (11) | 0.0603 (4) | |
O2 | 0.60919 (13) | 0.38214 (10) | 0.48790 (10) | 0.0518 (3) | |
C3 | 0.80659 (19) | 0.39383 (14) | 0.58372 (16) | 0.0508 (5) | |
C4 | 0.9331 (2) | 0.3953 (2) | 0.6029 (2) | 0.0735 (8) | |
H4 | 0.9717 | 0.4036 | 0.6676 | 0.0797 (19)* | |
C5 | 1.0116 (2) | 0.3864 (2) | 0.5430 (2) | 0.0904 (10) | |
H5 | 1.0941 | 0.3893 | 0.5735 | 0.0797 (19)* | |
C6 | 0.9857 (3) | 0.3742 (2) | 0.4466 (3) | 0.0949 (11) | |
H6 | 1.0521 | 0.3683 | 0.4194 | 0.0797 (19)* | |
C7 | 0.8722 (3) | 0.3695 (2) | 0.3838 (2) | 0.0856 (9) | |
H7 | 0.8724 | 0.3632 | 0.3190 | 0.0797 (19)* | |
C8 | 0.7586 (2) | 0.37284 (19) | 0.40271 (18) | 0.0693 (7) | |
H8 | 0.6941 | 0.3682 | 0.3483 | 0.0797 (19)* | |
C2 | 0.72321 (19) | 0.38201 (13) | 0.49018 (15) | 0.0481 (5) | |
C1 | 0.40782 (19) | 0.41923 (13) | 0.57321 (15) | 0.0463 (4) | |
O1 | 0.30587 (14) | 0.42580 (11) | 0.53975 (14) | 0.0673 (5) | |
C11 | 0.39501 (18) | 0.42413 (14) | 0.78808 (15) | 0.0485 (5) | |
C12 | 0.3303 (2) | 0.48760 (17) | 0.81636 (17) | 0.0583 (6) | |
H12 | 0.3629 | 0.5406 | 0.8238 | 0.0797 (19)* | |
C13 | 0.2156 (2) | 0.4727 (2) | 0.83403 (19) | 0.0737 (8) | |
H13 | 0.1728 | 0.5158 | 0.8535 | 0.0797 (19)* | |
C14 | 0.1669 (2) | 0.3961 (2) | 0.8230 (2) | 0.0800 (9) | |
H14 | 0.0914 | 0.3862 | 0.8360 | 0.0797 (19)* | |
C15 | 0.2293 (3) | 0.3326 (2) | 0.7924 (2) | 0.0861 (9) | |
H15 | 0.1947 | 0.2803 | 0.7832 | 0.0797 (19)* | |
C16 | 0.3433 (2) | 0.34595 (18) | 0.7751 (2) | 0.0715 (7) | |
H16 | 0.3850 | 0.3026 | 0.7549 | 0.0797 (19)* | |
C21 | 0.64010 (18) | 0.37610 (13) | 0.86772 (15) | 0.0446 (4) | |
C22 | 0.6066 (2) | 0.36832 (16) | 0.95464 (17) | 0.0611 (6) | |
H22 | 0.5360 | 0.3939 | 0.9624 | 0.0797 (19)* | |
C23 | 0.6775 (3) | 0.32272 (17) | 1.03030 (18) | 0.0680 (7) | |
H23 | 0.6544 | 0.3180 | 1.0883 | 0.0797 (19)* | |
C24 | 0.7821 (2) | 0.28451 (16) | 1.01927 (18) | 0.0655 (6) | |
H24 | 0.8302 | 0.2546 | 1.0700 | 0.0797 (19)* | |
C25 | 0.8149 (2) | 0.29079 (17) | 0.93319 (19) | 0.0663 (6) | |
H25 | 0.8849 | 0.2644 | 0.9254 | 0.0797 (19)* | |
C26 | 0.7444 (2) | 0.33635 (15) | 0.85749 (16) | 0.0546 (5) | |
H26 | 0.7676 | 0.3402 | 0.7994 | 0.0797 (19)* | |
C31 | 0.58254 (16) | 0.54313 (12) | 0.80681 (13) | 0.0404 (4) | |
C32 | 0.57133 (17) | 0.61243 (13) | 0.74251 (15) | 0.0456 (4) | |
H32 | 0.5535 | 0.6099 | 0.6754 | 0.0797 (19)* | |
C33 | 0.5922 (2) | 0.68529 (14) | 0.79899 (17) | 0.0544 (5) | |
H33 | 0.5902 | 0.7388 | 0.7751 | 0.0797 (19)* | |
C34 | 0.6165 (2) | 0.66308 (15) | 0.89754 (17) | 0.0571 (5) | |
H34 | 0.6328 | 0.6994 | 0.9496 | 0.0797 (19)* | |
C35 | 0.6116 (2) | 0.57584 (14) | 0.90337 (15) | 0.0510 (5) | |
H35 | 0.6250 | 0.5450 | 0.9600 | 0.0797 (19)* | |
C41A | 0.8865 (12) | 0.5283 (8) | 0.8392 (11) | 0.062 (2) | 0.611 (18) |
H41A | 0.8851 | 0.4709 | 0.8406 | 0.0797 (19)* | 0.611 (18) |
C42A | 0.8684 (8) | 0.5789 (9) | 0.7561 (7) | 0.065 (3) | 0.611 (18) |
H42A | 0.8508 | 0.5604 | 0.6925 | 0.0797 (19)* | 0.611 (18) |
C43A | 0.8815 (8) | 0.6607 (8) | 0.7854 (13) | 0.075 (4) | 0.611 (18) |
H43A | 0.8751 | 0.7057 | 0.7439 | 0.0797 (19)* | 0.611 (18) |
C44A | 0.9055 (9) | 0.6660 (7) | 0.8855 (14) | 0.083 (5) | 0.611 (18) |
H44A | 0.9178 | 0.7143 | 0.9219 | 0.0797 (19)* | 0.611 (18) |
C45A | 0.9078 (14) | 0.5839 (10) | 0.9223 (7) | 0.078 (4) | 0.611 (18) |
H45A | 0.9205 | 0.5688 | 0.9869 | 0.0797 (19)* | 0.611 (18) |
C45B | 0.899 (2) | 0.5532 (14) | 0.898 (2) | 0.106 (9) | 0.389 (18) |
H45B | 0.9122 | 0.5095 | 0.9414 | 0.0797 (19)* | 0.389 (18) |
C41B | 0.8744 (17) | 0.5460 (12) | 0.807 (3) | 0.097 (11) | 0.389 (18) |
H41B | 0.8626 | 0.4960 | 0.7738 | 0.0797 (19)* | 0.389 (18) |
C42B | 0.8681 (13) | 0.6206 (19) | 0.7645 (11) | 0.080 (7) | 0.389 (18) |
H42B | 0.8539 | 0.6298 | 0.6984 | 0.0797 (19)* | 0.389 (18) |
C44B | 0.9024 (18) | 0.637 (2) | 0.9232 (12) | 0.090 (8) | 0.389 (18) |
H44B | 0.9132 | 0.6596 | 0.9848 | 0.0797 (19)* | 0.389 (18) |
C43B | 0.8859 (17) | 0.6805 (10) | 0.8337 (17) | 0.065 (5) | 0.389 (18) |
H43B | 0.8870 | 0.7373 | 0.8245 | 0.0797 (19)* | 0.389 (18) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Rh | 0.03272 (7) | 0.04817 (9) | 0.03841 (8) | 0.00099 (6) | 0.00753 (6) | −0.00086 (6) |
Fe | 0.03644 (14) | 0.05011 (17) | 0.04330 (15) | −0.00207 (11) | 0.00686 (12) | 0.00505 (12) |
P | 0.0332 (2) | 0.0491 (3) | 0.0382 (2) | −0.00113 (19) | 0.00939 (19) | 0.0018 (2) |
O3 | 0.0360 (7) | 0.1023 (13) | 0.0419 (8) | −0.0010 (8) | 0.0081 (6) | 0.0028 (8) |
O2 | 0.0423 (7) | 0.0705 (10) | 0.0411 (7) | 0.0096 (7) | 0.0070 (6) | −0.0053 (7) |
C3 | 0.0398 (10) | 0.0653 (14) | 0.0485 (11) | 0.0043 (9) | 0.0132 (9) | 0.0126 (10) |
C4 | 0.0407 (11) | 0.121 (2) | 0.0595 (15) | 0.0028 (13) | 0.0142 (11) | 0.0178 (15) |
C5 | 0.0461 (13) | 0.145 (3) | 0.087 (2) | 0.0077 (16) | 0.0303 (14) | 0.032 (2) |
C6 | 0.0714 (19) | 0.137 (3) | 0.093 (2) | 0.0220 (19) | 0.0523 (18) | 0.029 (2) |
C7 | 0.088 (2) | 0.115 (3) | 0.0670 (17) | 0.0249 (19) | 0.0440 (16) | 0.0135 (17) |
C8 | 0.0665 (15) | 0.0939 (19) | 0.0499 (13) | 0.0203 (14) | 0.0190 (12) | 0.0007 (13) |
C2 | 0.0489 (11) | 0.0523 (12) | 0.0447 (11) | 0.0119 (9) | 0.0141 (9) | 0.0057 (9) |
C1 | 0.0453 (11) | 0.0448 (11) | 0.0483 (11) | 0.0002 (8) | 0.0105 (9) | −0.0013 (9) |
O1 | 0.0363 (8) | 0.0780 (12) | 0.0812 (12) | 0.0024 (7) | 0.0021 (8) | 0.0043 (9) |
C11 | 0.0358 (9) | 0.0680 (14) | 0.0415 (10) | −0.0044 (9) | 0.0092 (8) | 0.0078 (9) |
C12 | 0.0432 (11) | 0.0782 (16) | 0.0555 (13) | 0.0026 (11) | 0.0160 (10) | 0.0039 (11) |
C13 | 0.0408 (12) | 0.121 (2) | 0.0628 (15) | 0.0057 (14) | 0.0189 (11) | 0.0026 (15) |
C14 | 0.0399 (12) | 0.141 (3) | 0.0603 (15) | −0.0135 (15) | 0.0144 (11) | 0.0204 (17) |
C15 | 0.0575 (15) | 0.099 (2) | 0.100 (2) | −0.0277 (16) | 0.0151 (15) | 0.0195 (18) |
C16 | 0.0528 (13) | 0.0746 (17) | 0.0884 (19) | −0.0130 (12) | 0.0195 (13) | 0.0047 (15) |
C21 | 0.0424 (10) | 0.0455 (11) | 0.0438 (10) | −0.0032 (8) | 0.0063 (8) | 0.0028 (8) |
C22 | 0.0608 (14) | 0.0721 (16) | 0.0539 (13) | 0.0085 (12) | 0.0205 (11) | 0.0155 (11) |
C23 | 0.0788 (17) | 0.0744 (17) | 0.0511 (14) | 0.0045 (14) | 0.0162 (12) | 0.0173 (12) |
C24 | 0.0721 (16) | 0.0589 (14) | 0.0548 (14) | 0.0028 (12) | −0.0053 (12) | 0.0104 (11) |
C25 | 0.0580 (14) | 0.0723 (16) | 0.0635 (15) | 0.0187 (12) | 0.0050 (12) | 0.0023 (12) |
C26 | 0.0530 (12) | 0.0621 (14) | 0.0476 (12) | 0.0082 (10) | 0.0101 (10) | 0.0014 (10) |
C31 | 0.0347 (9) | 0.0490 (11) | 0.0386 (9) | 0.0000 (8) | 0.0111 (7) | 0.0020 (8) |
C32 | 0.0363 (9) | 0.0561 (12) | 0.0424 (10) | 0.0052 (8) | 0.0058 (8) | 0.0048 (9) |
C33 | 0.0485 (11) | 0.0504 (12) | 0.0643 (14) | 0.0055 (9) | 0.0137 (10) | 0.0031 (10) |
C34 | 0.0572 (13) | 0.0621 (14) | 0.0561 (13) | −0.0060 (10) | 0.0215 (11) | −0.0124 (11) |
C35 | 0.0539 (12) | 0.0614 (13) | 0.0410 (10) | −0.0080 (10) | 0.0177 (9) | −0.0007 (9) |
C41A | 0.042 (4) | 0.054 (4) | 0.094 (6) | 0.010 (3) | 0.026 (4) | 0.013 (4) |
C42A | 0.049 (3) | 0.083 (8) | 0.073 (4) | −0.002 (5) | 0.035 (3) | −0.004 (4) |
C43A | 0.048 (4) | 0.067 (7) | 0.118 (12) | −0.002 (5) | 0.034 (7) | 0.025 (7) |
C44A | 0.040 (3) | 0.073 (6) | 0.124 (12) | −0.009 (4) | −0.002 (8) | −0.029 (8) |
C45A | 0.057 (5) | 0.103 (11) | 0.064 (3) | 0.025 (8) | −0.007 (3) | −0.002 (6) |
C45B | 0.051 (6) | 0.081 (13) | 0.16 (2) | 0.013 (10) | −0.013 (16) | 0.036 (13) |
C41B | 0.040 (5) | 0.050 (10) | 0.19 (3) | 0.002 (6) | 0.015 (15) | −0.008 (12) |
C42B | 0.056 (5) | 0.12 (2) | 0.072 (6) | −0.010 (14) | 0.032 (4) | −0.035 (13) |
C44B | 0.043 (6) | 0.15 (2) | 0.071 (7) | −0.014 (11) | −0.002 (6) | −0.007 (12) |
C43B | 0.051 (7) | 0.058 (6) | 0.093 (15) | −0.015 (5) | 0.028 (9) | −0.010 (7) |
Rh—C1 | 1.803 (2) | C21—C22 | 1.387 (3) |
Rh—O3 | 2.0487 (14) | C22—C23 | 1.391 (3) |
Rh—O2 | 2.0838 (14) | C22—H22 | 0.9300 |
Rh—P | 2.2395 (5) | C23—C24 | 1.377 (4) |
Fe—C35 | 2.026 (2) | C23—H23 | 0.9300 |
Fe—C31 | 2.0400 (19) | C24—C25 | 1.370 (4) |
Fe—C32 | 2.041 (2) | C24—H24 | 0.9300 |
Fe—C34 | 2.045 (2) | C25—C26 | 1.389 (3) |
Fe—C33 | 2.047 (2) | C25—H25 | 0.9300 |
P—C31 | 1.798 (2) | C26—H26 | 0.9300 |
P—C11 | 1.8394 (19) | C31—C32 | 1.436 (3) |
P—C21 | 1.840 (2) | C31—C35 | 1.438 (3) |
O3—C3 | 1.295 (3) | C32—C33 | 1.416 (3) |
O2—C2 | 1.282 (2) | C32—H32 | 0.9300 |
C3—C4 | 1.390 (3) | C33—C34 | 1.412 (3) |
C3—C2 | 1.448 (3) | C33—H33 | 0.9300 |
C4—C5 | 1.381 (3) | C34—C35 | 1.418 (3) |
C4—H4 | 0.9300 | C34—H34 | 0.9300 |
C5—C6 | 1.350 (5) | C35—H35 | 0.9300 |
C5—H5 | 0.9300 | C41A—C42A | 1.414 (13) |
C6—C7 | 1.378 (5) | C41A—C45A | 1.463 (19) |
C6—H6 | 0.9300 | C41A—H41A | 0.9300 |
C7—C8 | 1.377 (4) | C42A—C43A | 1.387 (10) |
C7—H7 | 0.9300 | C42A—H42A | 0.9300 |
C8—C2 | 1.408 (3) | C43A—C44A | 1.390 (11) |
C8—H8 | 0.9300 | C43A—H43A | 0.9300 |
C1—O1 | 1.141 (2) | C44A—C45A | 1.428 (14) |
C11—C12 | 1.378 (3) | C44A—H44A | 0.9300 |
C11—C16 | 1.389 (3) | C45A—H45A | 0.9300 |
C12—C13 | 1.401 (3) | C45B—C41B | 1.26 (3) |
C12—H12 | 0.9300 | C45B—C44B | 1.41 (3) |
C13—C14 | 1.352 (4) | C45B—H45B | 0.9300 |
C13—H13 | 0.9300 | C41B—C42B | 1.35 (2) |
C14—C15 | 1.377 (5) | C41B—H41B | 0.9300 |
C14—H14 | 0.9300 | C42B—C43B | 1.364 (17) |
C15—C16 | 1.387 (4) | C42B—H42B | 0.9300 |
C15—H15 | 0.9300 | C44B—C43B | 1.43 (2) |
C16—H16 | 0.9300 | C44B—H44B | 0.9300 |
C21—C26 | 1.383 (3) | C43B—H43B | 0.9300 |
C1—Rh—O3 | 172.71 (8) | C24—C23—H23 | 120.0 |
C1—Rh—O2 | 95.98 (8) | C22—C23—H23 | 120.0 |
O3—Rh—O2 | 77.56 (6) | C25—C24—C23 | 119.7 (2) |
C1—Rh—P | 89.73 (7) | C25—C24—H24 | 120.1 |
O3—Rh—P | 96.75 (4) | C23—C24—H24 | 120.1 |
O2—Rh—P | 174.29 (4) | C24—C25—C26 | 120.5 (2) |
C35—Fe—C31 | 41.40 (8) | C24—C25—H25 | 119.8 |
C35—Fe—C32 | 69.06 (9) | C26—C25—H25 | 119.8 |
C31—Fe—C32 | 41.20 (8) | C21—C26—C25 | 120.6 (2) |
C35—Fe—C34 | 40.76 (9) | C21—C26—H26 | 119.7 |
C31—Fe—C34 | 69.04 (8) | C25—C26—H26 | 119.7 |
C32—Fe—C34 | 68.41 (9) | C32—C31—C35 | 106.73 (18) |
C35—Fe—C33 | 68.46 (9) | C32—C31—P | 124.39 (15) |
C31—Fe—C33 | 68.83 (9) | C35—C31—P | 128.53 (15) |
C32—Fe—C33 | 40.54 (9) | C32—C31—Fe | 69.46 (11) |
C34—Fe—C33 | 40.37 (9) | C35—C31—Fe | 68.79 (11) |
C31—P—C11 | 102.22 (9) | P—C31—Fe | 131.79 (10) |
C31—P—C21 | 104.11 (9) | C33—C32—C31 | 108.16 (18) |
C11—P—C21 | 100.95 (9) | C33—C32—Fe | 69.96 (12) |
C31—P—Rh | 114.74 (6) | C31—C32—Fe | 69.34 (11) |
C11—P—Rh | 116.34 (7) | C33—C32—H32 | 125.9 |
C21—P—Rh | 116.42 (7) | C31—C32—H32 | 125.9 |
C3—O3—Rh | 115.32 (13) | Fe—C32—H32 | 126.4 |
C2—O2—Rh | 114.13 (13) | C34—C33—C32 | 108.6 (2) |
O3—C3—C4 | 117.8 (2) | C34—C33—Fe | 69.72 (13) |
O3—C3—C2 | 115.82 (18) | C32—C33—Fe | 69.51 (12) |
C4—C3—C2 | 126.3 (2) | C34—C33—H33 | 125.7 |
C5—C4—C3 | 131.5 (3) | C32—C33—H33 | 125.7 |
C5—C4—H4 | 114.3 | Fe—C33—H33 | 126.7 |
C3—C4—H4 | 114.3 | C33—C34—C35 | 108.2 (2) |
C6—C5—C4 | 129.2 (3) | C33—C34—Fe | 69.91 (12) |
C6—C5—H5 | 115.4 | C35—C34—Fe | 68.92 (12) |
C4—C5—H5 | 115.4 | C33—C34—H34 | 125.9 |
C5—C6—C7 | 127.5 (3) | C35—C34—H34 | 125.9 |
C5—C6—H6 | 116.2 | Fe—C34—H34 | 126.8 |
C7—C6—H6 | 116.2 | C34—C35—C31 | 108.33 (19) |
C6—C7—C8 | 129.5 (3) | C34—C35—Fe | 70.32 (12) |
C6—C7—H7 | 115.2 | C31—C35—Fe | 69.80 (11) |
C8—C7—H7 | 115.2 | C34—C35—H35 | 125.8 |
C7—C8—C2 | 131.1 (3) | C31—C35—H35 | 125.8 |
C7—C8—H8 | 114.4 | Fe—C35—H35 | 125.6 |
C2—C8—H8 | 114.4 | C42A—C41A—C45A | 106.5 (10) |
O2—C2—C8 | 118.6 (2) | C42A—C41A—H41A | 126.7 |
O2—C2—C3 | 116.70 (18) | C45A—C41A—H41A | 126.8 |
C8—C2—C3 | 124.7 (2) | C41A—C42A—C43A | 108.6 (10) |
O1—C1—Rh | 177.0 (2) | C41A—C42A—H42A | 125.7 |
C12—C11—C16 | 118.9 (2) | C43A—C42A—H42A | 125.7 |
C12—C11—P | 122.65 (17) | C44A—C43A—C42A | 110.4 (9) |
C16—C11—P | 118.42 (18) | C44A—C43A—H43A | 124.8 |
C11—C12—C13 | 120.3 (3) | C42A—C43A—H43A | 124.8 |
C11—C12—H12 | 119.9 | C43A—C44A—C45A | 107.6 (7) |
C13—C12—H12 | 119.9 | C43A—C44A—H44A | 126.2 |
C14—C13—C12 | 120.4 (3) | C45A—C44A—H44A | 126.2 |
C14—C13—H13 | 119.8 | C41A—C45A—C44A | 106.9 (8) |
C12—C13—H13 | 119.8 | C41A—C45A—H45A | 126.5 |
C13—C14—C15 | 119.7 (2) | C44A—C45A—H45A | 126.6 |
C13—C14—H14 | 120.1 | C41B—C45B—C44B | 109.9 (16) |
C15—C14—H14 | 120.1 | C41B—C45B—H45B | 125.0 |
C14—C15—C16 | 120.7 (3) | C44B—C45B—H45B | 125.1 |
C14—C15—H15 | 119.6 | C45B—C41B—C42B | 110.6 (17) |
C16—C15—H15 | 119.6 | C45B—C41B—H41B | 124.7 |
C15—C16—C11 | 119.8 (3) | C42B—C41B—H41B | 124.6 |
C15—C16—H16 | 120.1 | C43B—C42B—C41B | 109.4 (16) |
C11—C16—H16 | 120.1 | C43B—C42B—H42B | 125.2 |
C26—C21—C22 | 118.5 (2) | C41B—C42B—H42B | 125.3 |
C26—C21—P | 120.62 (16) | C45B—C44B—C43B | 104.8 (18) |
C22—C21—P | 120.88 (16) | C45B—C44B—H44B | 127.5 |
C21—C22—C23 | 120.7 (2) | C43B—C44B—H44B | 127.6 |
C21—C22—H22 | 119.6 | C42B—C43B—C44B | 105.1 (17) |
C23—C22—H22 | 119.6 | C42B—C43B—H43B | 127.5 |
C24—C23—C22 | 120.0 (2) | C44B—C43B—H43B | 127.4 |
Rh—P—C31—C41A | −72.3 (2) | C42B—C43B—C34—C33 | −61.3 (18) |
Rh—P—C31—C41B | −63.5 (6) | C43A—C44A—C34—C33 | −18.4 (8) |
C45B—C41B—C32—C31 | −58.6 (16) | C43B—C44B—C35—C34 | −58.1 (19) |
C41A—C42A—C32—C31 | −16.1 (10) | C44A—C45A—C35—C34 | −17.8 (9) |
C41B—C42B—C33—C32 | −60.6 (17) | C44B—C45B—C31—C35 | −53.6 (18) |
C42A—C43A—C33—C32 | −16.6 (8) | C45A—C41A—C31—C35 | −16.1 (8) |
Experimental details
Crystal data | |
Chemical formula | [Rh(C7H5O2)(C22H19FeP)(CO)] |
Mr | 622.22 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 11.3122 (7), 16.2035 (9), 14.2663 (8) |
β (°) | 104.046 (10) |
V (Å3) | 2536.8 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.32 |
Crystal size (mm) | 0.30 × 0.26 × 0.20 |
Data collection | |
Diffractometer | Siemens SMART CCD 1K diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.694, 0.779 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 27848, 6239, 5239 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.062, 1.08 |
No. of reflections | 6239 |
No. of parameters | 373 |
No. of restraints | 42 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.26, −0.38 |
Computer programs: SMART (Siemens, 1995), SMART, SHELXTL (Siemens, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 1999), SHELXL97.
Rh—C1 | 1.803 (2) | Rh—P | 2.2395 (5) |
Rh—O3 | 2.0487 (14) | C1—O1 | 1.141 (2) |
Rh—O2 | 2.0838 (14) | ||
C1—Rh—O3 | 172.71 (8) | O3—Rh—P | 96.75 (4) |
C1—Rh—O2 | 95.98 (8) | O2—Rh—P | 174.29 (4) |
O3—Rh—O2 | 77.56 (6) | O1—C1—Rh | 177.0 (2) |
C1—Rh—P | 89.73 (7) | ||
Rh—P—C31—C41A | −72.3 (2) | Rh—P—C31—C41B | −63.5 (6) |
Complex | Rh-O3a | Rh-O2b | Rh-P | O3-Rh-O2 |
[Rh(trop)(CO)(PFcPh2)]c | 2.0487 (14) | 2.0838 (14) | 2.2395 (5) | 77.56 (6) |
[Rh(trop)(CO)(PPh3)]d | 2.034 (7) | 2.081 (7) | 2.232 (2) | 77.8 (3) |
[Rh(cupf)(CO)(PPh3)]e | 2.024 (6) | 2.063 (6) | 2.232 (3) | 76.6 (3) |
Notes: (i) bidentate oxygen ligand forming five membered chelate, (a) oxygen atom trans to the carbonyl, (b) oxygen atom trans to the phosphine, (c) present study, (d) Leipoldt et al. (1980), (e) Basson et al. (1986), |
L | ν(CO) (KBr/cm-1) | ν(CO) (CH2Cl2/cm-1) | 1J(Rh-P) (Hz) | pKaa |
P(p-CH3-Ph)3 | 1966 | 1973 | 175 | 3.84 |
PFcPh2 | 1965 | 1974 | 174 | |
PPh3 | 1974 | 1975 | 173 | 2.73 |
P(p-F-Ph)3 | 1975 | 1976 | 172 | 1.97 |
Notes: (a) Wilkinson (1987). |
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A large number of rhodium(I) complexes are known, of which many involve π-bonding ligands such as CO, phosphines and arenes. A subset of these compounds includes β-diketonate and tropolonate. In this paper, we report the structure of [Rh(trop)(CO)(PFcPh2)], (I), as another complex in this series containing a ferrocenyl-functionalized tertiary phosphine.
The title compound crystallizes as a distorted square-planar moiety (Fig. 1) with the most important bond distances and angles given in Table 1. The efficient packing in the crystal structure is illustrated by the closest intermolecular contact of 2.91 Å between the rhodium centre and H43b(1.5 - x, -0.5 + y, 1.5 - z).
The Rh—P bond of 2.2395 (5) Å is comparable with that found in the corresponding [Rh(trop)(CO)(PPh3)] and [Rh(cupf)(CO)(PPh3)] (cupf = N-hydroxy-N-nitrosobenzeneaminato-O,O') complexes, see Table 2. The Rh—O2 bond is significantly longer than the Rh—O3 bond due to the larger trans influence of PFcPh2 compared with CO. The small steric demand of the tropolonate ligand is illustrated by the small O2—Rh—O3 bite angle of 77.56 (6)° and the consequent O3—Rh—P, O2—Rh—C1 and P—Rh—C1 coordination angles of 96.75 (4), 95.98 (8) and 89.73 (7)°, respectively. To date, [Rh(cupf)(CO)(PPh3)] is the only analogous complex, containing a five-membered O,O-chelate, for which a smaller O—Rh—O bite angle has been reported (Basson et al., 1986), see Table 2. A slight elongation is observed in the Rh—O2 and Rh—O3 bonds compared with similar complexes. The RhI centre is only slightly displaced by a distance of 0.0308 (8) Å from the plane defined by the four donor atoms of the respective ligands.
The variation in electron density of the RhI centre as a function of the substituent X on the tertiary aryl phosphine PX3 is illustrated by the slight decrease of the carbonyl stretching frequency. This arises as an increase in the electron density on the rhodium centre results in increased back donation to the carbonyl C atom which in turn lowers ν(CO). This is illustrated for both the solid-state and liquid-state data presented in Table 3, which are in agreement with the trend in basicity of the tertiary phospines as reflected in the respective pKa values.
It was reported Steyn et al. (1997) and extended to a wider range by Roodt & Steyn (2000) that the first order Rh—P coupling constants, 1J(Rh—P), in rhodium–phosphine complexes, determined from 31P NMR, enable good estimations of the Rh—P bond strength. Although small, a tendency is observed in Table 3, indicating PFcPh2 to be better electron donating than PPh3, and comparable to P(p—CH3—Ph)3.
The torsion angles of -72.3 (2) and -63.5 (6)° for Rh—P—C31—C41a and Rh—P—C31—C41b illustrate the different orientations of the ferrocenyl moiety (see Experimental), and is also related to the solid-state steric demand of the PFcPh2 ligand (Otto et al., 2000). In this regard, effective (using the actual Rh—P bond distance) and Tolman-cone angles (using a Rh—P bond distance of 2.28 Å; Tolman, 1977) of 171.2 and 169.8° for orientation β1, and 167.4 and 166.1° for orientation β2, were calculated.