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metal-organic compounds
(+)-{1,2-Bis[(2R,5R)-2,5-diethylphospholan-1-yl]ethane-κ2P,P′}(η4-cycloocta-1,5-diene)rhodium(I) tetrafluoridoborate
aLeibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Str. 29a, 18059 Rostock, Germany
*Correspondence e-mail: hans-joachim.drexler@catalysis.de
The title compound, [Rh(C8H12)(C18H36P2)]BF4, exhibits a rhodium(I) complex cation with a bidentate bisphosphine ligand and a bidentate η2,η2-coordinated cycloocta-1,5-diene ligand. The ligands form a slightly distorted square-planar coordination environment for the Rh(I) atom. An intramolecular P–Rh–P bite angle of 83.91 (2)° is observed. The dihedral angle between the P—Rh—P and the X—Rh—X planes (X is the centroid of a double bond) is 14.0 (1)°. The BF4 anion is disordered over two positions in a 0.515 (7):0.485 (7) ratio.
Related literature
For general synthetic aspects and different related structures of cationic rhodium bisphosphine diolefin complexes, see: Schulz et al. (2010) and references cited therein. For applications of the Et-BPE ligand {Et-BPE (1,2-bis[(2R,5R)-2,5-diethylphospholan-1-yl]ethane)} in catalytic reactions, see: Axtell et al. (2005
); Jerphagnon et al. (2003
); Burk et al. (1998
). For related structures, see: Burk et al. (1990
); Drexler et al. (2001
, 2004
).
Experimental
Crystal data
|
Data collection: X-AREA (Stoe & Cie, 2005); cell X-AREA
; data reduction: X-RED32 (Stoe & Cie, 2005)
; 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/S1600536810039577/si2281sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810039577/si2281Isup2.hkl
By overlaying a solution of [Rh((R,R)-Et-BPE)COD)]BF4 in dichloromethane with MTBE (methyl-tert-butylether) red single crystals suitable for X-ray analysis are obtained. 31P NMR (CD2Cl2, 298 K, 162 MHz) [p.p.m.]: 73.5 (d, JP—Rh = 145.5 Hz).
All non-hydrogen atoms are refined anisotropically, except not fully occupied fluorine atoms of the anion. All H atoms were placed in idealized positions with d(C—H) = 0.98(CH), 0.97 (CH2) and 0.96 (CH3) Å and refined using a riding model with Uiso(H) fixed at 1.5 Ueq(C) for CH3 and 1.2 Ueq(C) for CH2 and CH. The
indicators 2R,5R for the title compound were determined by using 2621 Friedel pairs in the The at convergence was -0.02 (2).The geometry of the cation of the title compound is comparable with the three independent complexes described in Schulz et al. (2010): the dihedral angle between the planes P1,Rh1,P2 and X1,Rh1,X2 (X = centroid of the double bond) of 14.0 (1)° corresponds to those in the Me-BPE complexes (14.7 (1)°, 14.8 (1)° and 15.3 (1)°). Furthermore, the dihedral angle is not the value found for the corresponding Et-DuPhos complex [Rh((R,R)-Et-DuPhos)COD]BF4 (21.1 (1)°) (Drexler et al., 2001) or for the complex [Rh((R,R)-Me-BPE)COD]SbF6 (19.4°) (Burk et al., 1990; Drexler et al., 2004). The cationic rhodium bisphosphine diolefine complexes build up five-membered ring chelates with rhodium (Fig. 1). For the title compound the molecular structure shows a δ-conformation of the backbone of the bisphosphine. The COD is η2,η2-coordinated and is orientated in an anticlockwise twist manner. An intramolecular P1—Rh1—P2 angle of 83.91 (2)° is obtained. This is in the same range of corresponding complexes already described in the literature Schulz et al. (2010) and literature therein. The bonds Rh1—P1 and Rh1—P2 show bond lengths of 2.2754 (8) Å and 2.2702 (8) Å, respectively. Applications of the ligand Et-BPE in catalytic reactions are reported by Axtell et al. (2005); Jerphagnon et al. (2003) and Burk et al. (1998).
For general synthetic aspects and different related structures of cationic rhodium bisphosphine diolefin complexes, see: Schulz et al. (2010) and references cited therein. For applications of the Et-BPE ligand in catalytic reactions, see: Axtell et al. (2005); Jerphagnon et al. (2003); Burk et al. (1998). For related structures, see: Burk et al. (1990); Drexler et al. (2001, 2004).
Data collection: X-AREA (Stoe & Cie, 2005); cell
X-AREA (Stoe & Cie, 2005); data reduction: X-RED32 (Stoe & Cie, 2005); 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. Perspective view and numbering scheme of the cation [Rh((R,R)-Et-BPE)COD]+. All H atoms and the anion have been omitted for clarity. Thermal ellipsoids are drawn at the 30% probability level. |
[Rh(C8H12)(C18H36P2)]BF4 | F(000) = 1280 |
Mr = 612.32 | Dx = 1.423 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 54003 reflections |
a = 8.8374 (18) Å | θ = 1.6–27.2° |
b = 16.218 (3) Å | µ = 0.75 mm−1 |
c = 19.946 (4) Å | T = 200 K |
V = 2858.7 (10) Å3 | Part of block, red |
Z = 4 | 0.50 × 0.43 × 0.40 mm |
STOE IPDS 2 diffractometer | 6075 independent reflections |
Radiation source: fine-focus sealed tube | 5779 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
Detector resolution: 6.67 pixels mm-1 | θmax = 26.8°, θmin = 1.6° |
rotation method scans | h = −11→11 |
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 2005) | k = −20→20 |
Tmin = 0.728, Tmax = 0.858 | l = −25→25 |
36650 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)] = 0.027 | H-atom parameters constrained |
wR(F2) = 0.073 | w = 1/[σ2(Fo2) + (0.0545P)2 + 0.2291P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.002 |
6075 reflections | Δρmax = 0.95 e Å−3 |
305 parameters | Δρmin = −0.34 e Å−3 |
21 restraints | Absolute structure: Flack (1983), 2621 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.02 (2) |
[Rh(C8H12)(C18H36P2)]BF4 | V = 2858.7 (10) Å3 |
Mr = 612.32 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 8.8374 (18) Å | µ = 0.75 mm−1 |
b = 16.218 (3) Å | T = 200 K |
c = 19.946 (4) Å | 0.50 × 0.43 × 0.40 mm |
STOE IPDS 2 diffractometer | 6075 independent reflections |
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 2005) | 5779 reflections with I > 2σ(I) |
Tmin = 0.728, Tmax = 0.858 | Rint = 0.035 |
36650 measured reflections |
R[F2 > 2σ(F2)] = 0.027 | H-atom parameters constrained |
wR(F2) = 0.073 | Δρmax = 0.95 e Å−3 |
S = 1.06 | Δρmin = −0.34 e Å−3 |
6075 reflections | Absolute structure: Flack (1983), 2621 Friedel pairs |
305 parameters | Absolute structure parameter: −0.02 (2) |
21 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 | Occ. (<1) | |
Rh1 | 0.55265 (2) | 0.179334 (12) | 0.820495 (9) | 0.02703 (6) | |
P1 | 0.62151 (8) | 0.15079 (4) | 0.71305 (3) | 0.02599 (13) | |
P2 | 0.62220 (8) | 0.04667 (4) | 0.83972 (3) | 0.02676 (13) | |
C1 | 0.5242 (4) | 0.31550 (18) | 0.80272 (15) | 0.0417 (7) | |
H1A | 0.5663 | 0.3348 | 0.7600 | 0.050* | |
C2 | 0.3872 (4) | 0.2772 (2) | 0.79692 (15) | 0.0431 (7) | |
H2A | 0.3502 | 0.2749 | 0.7506 | 0.052* | |
C3 | 0.2629 (5) | 0.2709 (3) | 0.8481 (2) | 0.0656 (11) | |
H3A | 0.1969 | 0.2254 | 0.8362 | 0.079* | |
H3B | 0.2032 | 0.3211 | 0.8470 | 0.079* | |
C4 | 0.3214 (6) | 0.2576 (3) | 0.9195 (2) | 0.0721 (13) | |
H4A | 0.3489 | 0.3106 | 0.9384 | 0.087* | |
H4B | 0.2401 | 0.2351 | 0.9466 | 0.087* | |
C5 | 0.4564 (6) | 0.2006 (2) | 0.92417 (14) | 0.0550 (10) | |
H5A | 0.4380 | 0.1500 | 0.9499 | 0.066* | |
C6 | 0.6040 (6) | 0.2249 (2) | 0.92248 (16) | 0.0555 (11) | |
H6A | 0.6720 | 0.1888 | 0.9479 | 0.067* | |
C7 | 0.6635 (7) | 0.3112 (2) | 0.91348 (19) | 0.0689 (13) | |
H7A | 0.7685 | 0.3079 | 0.8995 | 0.083* | |
H7B | 0.6612 | 0.3389 | 0.9566 | 0.083* | |
C8 | 0.5783 (6) | 0.3636 (2) | 0.86315 (19) | 0.0667 (13) | |
H8A | 0.4916 | 0.3883 | 0.8852 | 0.080* | |
H8B | 0.6437 | 0.4080 | 0.8481 | 0.080* | |
C9 | 0.6456 (3) | 0.03874 (18) | 0.70368 (13) | 0.0333 (6) | |
H9A | 0.5478 | 0.0122 | 0.6988 | 0.040* | |
H9B | 0.7057 | 0.0267 | 0.6642 | 0.040* | |
C10 | 0.7254 (3) | 0.00717 (18) | 0.76640 (13) | 0.0340 (6) | |
H10A | 0.8294 | 0.0264 | 0.7672 | 0.041* | |
H10B | 0.7259 | −0.0526 | 0.7668 | 0.041* | |
C11 | 0.5147 (3) | 0.18501 (18) | 0.63828 (12) | 0.0309 (5) | |
H11A | 0.4830 | 0.2421 | 0.6462 | 0.037* | |
C12 | 0.6369 (4) | 0.1865 (2) | 0.58392 (14) | 0.0435 (7) | |
H12A | 0.6605 | 0.1308 | 0.5696 | 0.052* | |
H12B | 0.6018 | 0.2174 | 0.5453 | 0.052* | |
C13 | 0.7764 (4) | 0.2272 (2) | 0.61365 (17) | 0.0484 (8) | |
H13A | 0.7610 | 0.2863 | 0.6161 | 0.058* | |
H13B | 0.8631 | 0.2168 | 0.5850 | 0.058* | |
C14 | 0.8070 (3) | 0.19301 (18) | 0.68390 (14) | 0.0364 (6) | |
H14A | 0.8773 | 0.1466 | 0.6793 | 0.044* | |
C15 | 0.3730 (4) | 0.1352 (2) | 0.62165 (15) | 0.0414 (7) | |
H15A | 0.3083 | 0.1328 | 0.6609 | 0.050* | |
H15B | 0.4020 | 0.0793 | 0.6102 | 0.050* | |
C16 | 0.2847 (4) | 0.1727 (3) | 0.56339 (17) | 0.0522 (8) | |
H16A | 0.1960 | 0.1402 | 0.5549 | 0.078* | |
H16B | 0.3473 | 0.1735 | 0.5241 | 0.078* | |
H16C | 0.2553 | 0.2280 | 0.5746 | 0.078* | |
C17 | 0.8803 (4) | 0.2564 (3) | 0.7303 (2) | 0.0556 (9) | |
H17A | 0.8119 | 0.3026 | 0.7362 | 0.067* | |
H17B | 0.8971 | 0.2316 | 0.7739 | 0.067* | |
C18 | 1.0305 (5) | 0.2877 (3) | 0.7027 (3) | 0.0729 (12) | |
H18A | 1.0730 | 0.3272 | 0.7333 | 0.109* | |
H18B | 1.0140 | 0.3135 | 0.6600 | 0.109* | |
H18C | 1.0991 | 0.2423 | 0.6975 | 0.109* | |
C19 | 0.7298 (3) | 0.01375 (18) | 0.91399 (14) | 0.0338 (6) | |
H19A | 0.6911 | 0.0451 | 0.9523 | 0.041* | |
C20 | 0.6821 (4) | −0.07572 (19) | 0.92375 (17) | 0.0449 (7) | |
H20A | 0.7293 | −0.1108 | 0.8903 | 0.054* | |
H20B | 0.7111 | −0.0951 | 0.9679 | 0.054* | |
C21 | 0.5106 (4) | −0.07681 (19) | 0.91604 (16) | 0.0428 (7) | |
H21A | 0.4637 | −0.0499 | 0.9542 | 0.051* | |
H21B | 0.4747 | −0.1333 | 0.9143 | 0.051* | |
C22 | 0.4677 (3) | −0.03148 (17) | 0.85109 (14) | 0.0345 (6) | |
H22A | 0.4750 | −0.0711 | 0.8141 | 0.041* | |
C23 | 0.3065 (4) | 0.0006 (2) | 0.85289 (17) | 0.0448 (7) | |
H23A | 0.3000 | 0.0436 | 0.8865 | 0.054* | |
H23B | 0.2402 | −0.0439 | 0.8668 | 0.054* | |
C24 | 0.2487 (4) | 0.0349 (3) | 0.7865 (2) | 0.0622 (10) | |
H24A | 0.1466 | 0.0540 | 0.7920 | 0.093* | |
H24B | 0.2513 | −0.0076 | 0.7530 | 0.093* | |
H24C | 0.3118 | 0.0800 | 0.7727 | 0.093* | |
C25 | 0.9010 (4) | 0.0292 (2) | 0.91028 (17) | 0.0456 (7) | |
H25A | 0.9430 | −0.0031 | 0.8738 | 0.055* | |
H25B | 0.9186 | 0.0869 | 0.9003 | 0.055* | |
C26 | 0.9818 (5) | 0.0075 (4) | 0.9735 (2) | 0.0775 (13) | |
H26A | 1.0879 | 0.0184 | 0.9683 | 0.116* | |
H26B | 0.9669 | −0.0499 | 0.9832 | 0.116* | |
H26C | 0.9425 | 0.0401 | 1.0097 | 0.116* | |
B1 | 0.5008 (3) | 0.0287 (2) | 0.09541 (15) | 0.0521 (9) | |
F1 | 0.4824 (5) | 0.0657 (3) | 0.15617 (16) | 0.1419 (18) | |
F2 | 0.4003 (6) | 0.0460 (4) | 0.0449 (2) | 0.0663 (15)* | 0.515 (7) |
F3 | 0.6464 (5) | 0.0467 (4) | 0.0748 (3) | 0.0791 (18)* | 0.515 (7) |
F4 | 0.4794 (10) | −0.0470 (4) | 0.1253 (4) | 0.125 (3)* | 0.515 (7) |
F2' | 0.3620 (5) | 0.0229 (4) | 0.0636 (3) | 0.0655 (15)* | 0.485 (7) |
F3' | 0.5818 (10) | 0.0895 (5) | 0.0629 (4) | 0.111 (3)* | 0.485 (7) |
F4' | 0.5614 (7) | −0.0489 (3) | 0.0851 (3) | 0.0781 (19)* | 0.485 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Rh1 | 0.03754 (10) | 0.02407 (10) | 0.01948 (9) | 0.00346 (8) | −0.00143 (7) | −0.00007 (7) |
P1 | 0.0289 (3) | 0.0278 (3) | 0.0213 (3) | 0.0005 (2) | 0.0010 (2) | 0.0001 (2) |
P2 | 0.0317 (3) | 0.0240 (3) | 0.0246 (3) | 0.0016 (3) | −0.0005 (2) | 0.0006 (2) |
C1 | 0.0641 (19) | 0.0273 (13) | 0.0336 (13) | 0.0106 (14) | −0.0043 (12) | 0.0059 (11) |
C2 | 0.0526 (17) | 0.0443 (17) | 0.0324 (13) | 0.0261 (15) | 0.0063 (13) | 0.0056 (12) |
C3 | 0.062 (2) | 0.076 (3) | 0.059 (2) | 0.030 (2) | 0.0252 (19) | 0.006 (2) |
C4 | 0.107 (4) | 0.065 (3) | 0.044 (2) | 0.028 (2) | 0.037 (2) | 0.0032 (18) |
C5 | 0.104 (3) | 0.0408 (18) | 0.0198 (12) | 0.0109 (19) | 0.0115 (17) | 0.0005 (11) |
C6 | 0.111 (3) | 0.0291 (16) | 0.0265 (14) | 0.0103 (18) | −0.0235 (17) | −0.0037 (12) |
C7 | 0.126 (4) | 0.0322 (18) | 0.0481 (19) | −0.002 (2) | −0.034 (2) | −0.0029 (15) |
C8 | 0.124 (4) | 0.0303 (17) | 0.0455 (18) | 0.002 (2) | −0.015 (2) | 0.0045 (14) |
C9 | 0.0405 (15) | 0.0334 (14) | 0.0260 (12) | 0.0011 (11) | 0.0036 (10) | −0.0019 (11) |
C10 | 0.0411 (15) | 0.0310 (14) | 0.0299 (13) | 0.0040 (11) | 0.0038 (11) | −0.0001 (11) |
C11 | 0.0391 (14) | 0.0326 (13) | 0.0210 (10) | 0.0000 (11) | −0.0007 (9) | 0.0014 (10) |
C12 | 0.0479 (17) | 0.057 (2) | 0.0253 (12) | 0.0031 (16) | 0.0055 (11) | 0.0059 (13) |
C13 | 0.0458 (17) | 0.061 (2) | 0.0386 (16) | −0.0046 (15) | 0.0080 (13) | 0.0160 (15) |
C14 | 0.0327 (13) | 0.0392 (15) | 0.0371 (14) | 0.0000 (10) | 0.0009 (11) | 0.0051 (12) |
C15 | 0.0480 (17) | 0.0448 (17) | 0.0314 (14) | −0.0022 (14) | −0.0072 (12) | 0.0045 (12) |
C16 | 0.0573 (19) | 0.057 (2) | 0.0426 (16) | −0.0054 (18) | −0.0188 (14) | 0.0081 (17) |
C17 | 0.0420 (17) | 0.063 (2) | 0.062 (2) | −0.0173 (17) | 0.0009 (16) | −0.0054 (18) |
C18 | 0.047 (2) | 0.085 (3) | 0.087 (3) | −0.024 (2) | −0.0018 (19) | 0.002 (2) |
C19 | 0.0390 (15) | 0.0329 (15) | 0.0294 (13) | 0.0031 (11) | −0.0023 (11) | 0.0043 (11) |
C20 | 0.060 (2) | 0.0308 (15) | 0.0440 (17) | 0.0067 (14) | −0.0009 (15) | 0.0087 (13) |
C21 | 0.0573 (19) | 0.0299 (14) | 0.0412 (15) | −0.0087 (13) | 0.0024 (13) | 0.0082 (12) |
C22 | 0.0418 (16) | 0.0282 (13) | 0.0335 (12) | −0.0061 (12) | 0.0032 (11) | −0.0025 (10) |
C23 | 0.0369 (16) | 0.0483 (18) | 0.0491 (18) | −0.0052 (13) | 0.0065 (13) | 0.0055 (15) |
C24 | 0.0378 (18) | 0.083 (3) | 0.066 (2) | −0.0052 (18) | −0.0062 (16) | 0.014 (2) |
C25 | 0.0435 (17) | 0.0484 (19) | 0.0450 (17) | 0.0009 (13) | −0.0045 (13) | 0.0088 (14) |
C26 | 0.066 (3) | 0.106 (4) | 0.061 (3) | −0.001 (2) | −0.012 (2) | 0.010 (2) |
B1 | 0.061 (2) | 0.045 (2) | 0.050 (2) | −0.0017 (17) | −0.0056 (17) | 0.0075 (17) |
F1 | 0.118 (3) | 0.241 (5) | 0.0664 (18) | −0.026 (3) | 0.0212 (19) | −0.049 (3) |
Rh1—C2 | 2.209 (3) | C13—H13B | 0.9700 |
Rh1—C6 | 2.211 (3) | C14—C17 | 1.528 (5) |
Rh1—C1 | 2.251 (3) | C14—H14A | 0.9800 |
Rh1—C5 | 2.262 (3) | C15—C16 | 1.526 (4) |
Rh1—P2 | 2.2702 (8) | C15—H15A | 0.9700 |
Rh1—P1 | 2.2754 (8) | C15—H15B | 0.9700 |
P1—C9 | 1.839 (3) | C16—H16A | 0.9600 |
P1—C11 | 1.850 (3) | C16—H16B | 0.9600 |
P1—C14 | 1.869 (3) | C16—H16C | 0.9600 |
P2—C10 | 1.839 (3) | C17—C18 | 1.524 (5) |
P2—C19 | 1.840 (3) | C17—H17A | 0.9700 |
P2—C22 | 1.877 (3) | C17—H17B | 0.9700 |
C1—C2 | 1.366 (5) | C18—H18A | 0.9600 |
C1—C8 | 1.514 (5) | C18—H18B | 0.9600 |
C1—H1A | 0.9800 | C18—H18C | 0.9600 |
C2—C3 | 1.503 (5) | C19—C20 | 1.523 (4) |
C2—H2A | 0.9800 | C19—C25 | 1.536 (5) |
C3—C4 | 1.531 (6) | C19—H19A | 0.9800 |
C3—H3A | 0.9700 | C20—C21 | 1.524 (5) |
C3—H3B | 0.9700 | C20—H20A | 0.9700 |
C4—C5 | 1.511 (6) | C20—H20B | 0.9700 |
C4—H4A | 0.9700 | C21—C22 | 1.537 (4) |
C4—H4B | 0.9700 | C21—H21A | 0.9700 |
C5—C6 | 1.363 (7) | C21—H21B | 0.9700 |
C5—H5A | 0.9800 | C22—C23 | 1.517 (4) |
C6—C7 | 1.506 (5) | C22—H22A | 0.9800 |
C6—H6A | 0.9800 | C23—C24 | 1.524 (5) |
C7—C8 | 1.516 (5) | C23—H23A | 0.9700 |
C7—H7A | 0.9700 | C23—H23B | 0.9700 |
C7—H7B | 0.9700 | C24—H24A | 0.9600 |
C8—H8A | 0.9700 | C24—H24B | 0.9600 |
C8—H8B | 0.9700 | C24—H24C | 0.9600 |
C9—C10 | 1.525 (4) | C25—C26 | 1.491 (5) |
C9—H9A | 0.9700 | C25—H25A | 0.9700 |
C9—H9B | 0.9700 | C25—H25B | 0.9700 |
C10—H10A | 0.9700 | C26—H26A | 0.9600 |
C10—H10B | 0.9700 | C26—H26B | 0.9600 |
C11—C15 | 1.526 (4) | C26—H26C | 0.9600 |
C11—C12 | 1.531 (4) | B1—F1 | 1.362 (3) |
C11—H11A | 0.9800 | B1—F2 | 1.372 (4) |
C12—C13 | 1.518 (5) | B1—F4 | 1.377 (4) |
C12—H12A | 0.9700 | B1—F3' | 1.381 (4) |
C12—H12B | 0.9700 | B1—F3 | 1.382 (4) |
C13—C14 | 1.531 (4) | B1—F4' | 1.383 (4) |
C13—H13A | 0.9700 | B1—F2' | 1.384 (4) |
C2—Rh1—C6 | 95.24 (13) | C14—C13—H13A | 109.6 |
C2—Rh1—C1 | 35.65 (13) | C12—C13—H13B | 109.6 |
C6—Rh1—C1 | 80.79 (11) | C14—C13—H13B | 109.6 |
C2—Rh1—C5 | 80.57 (12) | H13A—C13—H13B | 108.2 |
C6—Rh1—C5 | 35.46 (17) | C17—C14—C13 | 112.7 (3) |
C1—Rh1—C5 | 87.29 (11) | C17—C14—P1 | 115.5 (2) |
C2—Rh1—P2 | 153.68 (10) | C13—C14—P1 | 105.2 (2) |
C6—Rh1—P2 | 96.08 (9) | C17—C14—H14A | 107.7 |
C1—Rh1—P2 | 170.65 (9) | C13—C14—H14A | 107.7 |
C5—Rh1—P2 | 95.26 (9) | P1—C14—H14A | 107.7 |
C2—Rh1—P1 | 97.05 (8) | C11—C15—C16 | 112.0 (3) |
C6—Rh1—P1 | 151.59 (13) | C11—C15—H15A | 109.2 |
C1—Rh1—P1 | 94.65 (8) | C16—C15—H15A | 109.2 |
C5—Rh1—P1 | 172.93 (13) | C11—C15—H15B | 109.2 |
P2—Rh1—P1 | 83.91 (2) | C16—C15—H15B | 109.2 |
C9—P1—C11 | 105.88 (13) | H15A—C15—H15B | 107.9 |
C9—P1—C14 | 103.23 (13) | C15—C16—H16A | 109.5 |
C11—P1—C14 | 94.99 (12) | C15—C16—H16B | 109.5 |
C9—P1—Rh1 | 109.13 (9) | H16A—C16—H16B | 109.5 |
C11—P1—Rh1 | 124.17 (9) | C15—C16—H16C | 109.5 |
C14—P1—Rh1 | 116.93 (10) | H16A—C16—H16C | 109.5 |
C10—P2—C19 | 106.43 (13) | H16B—C16—H16C | 109.5 |
C10—P2—C22 | 102.82 (13) | C18—C17—C14 | 112.0 (3) |
C19—P2—C22 | 94.75 (13) | C18—C17—H17A | 109.2 |
C10—P2—Rh1 | 109.28 (9) | C14—C17—H17A | 109.2 |
C19—P2—Rh1 | 123.44 (10) | C18—C17—H17B | 109.2 |
C22—P2—Rh1 | 117.61 (10) | C14—C17—H17B | 109.2 |
C2—C1—C8 | 125.6 (3) | H17A—C17—H17B | 107.9 |
C2—C1—Rh1 | 70.51 (16) | C17—C18—H18A | 109.5 |
C8—C1—Rh1 | 110.2 (2) | C17—C18—H18B | 109.5 |
C2—C1—H1A | 114.1 | H18A—C18—H18B | 109.5 |
C8—C1—H1A | 114.1 | C17—C18—H18C | 109.5 |
Rh1—C1—H1A | 114.1 | H18A—C18—H18C | 109.5 |
C1—C2—C3 | 128.4 (3) | H18B—C18—H18C | 109.5 |
C1—C2—Rh1 | 73.84 (17) | C20—C19—C25 | 115.7 (3) |
C3—C2—Rh1 | 106.9 (2) | C20—C19—P2 | 103.7 (2) |
C1—C2—H2A | 113.2 | C25—C19—P2 | 115.0 (2) |
C3—C2—H2A | 113.2 | C20—C19—H19A | 107.3 |
Rh1—C2—H2A | 113.2 | C25—C19—H19A | 107.3 |
C2—C3—C4 | 113.2 (4) | P2—C19—H19A | 107.3 |
C2—C3—H3A | 108.9 | C21—C20—C19 | 105.9 (3) |
C4—C3—H3A | 108.9 | C21—C20—H20A | 110.6 |
C2—C3—H3B | 108.9 | C19—C20—H20A | 110.6 |
C4—C3—H3B | 108.9 | C21—C20—H20B | 110.6 |
H3A—C3—H3B | 107.7 | C19—C20—H20B | 110.6 |
C5—C4—C3 | 114.2 (3) | H20A—C20—H20B | 108.7 |
C5—C4—H4A | 108.7 | C20—C21—C22 | 109.0 (3) |
C3—C4—H4A | 108.7 | C20—C21—H21A | 109.9 |
C5—C4—H4B | 108.7 | C22—C21—H21A | 109.9 |
C3—C4—H4B | 108.7 | C20—C21—H21B | 109.9 |
H4A—C4—H4B | 107.6 | C22—C21—H21B | 109.9 |
C6—C5—C4 | 125.2 (4) | H21A—C21—H21B | 108.3 |
C6—C5—Rh1 | 70.2 (2) | C23—C22—C21 | 112.1 (3) |
C4—C5—Rh1 | 109.5 (2) | C23—C22—P2 | 117.0 (2) |
C6—C5—H5A | 114.4 | C21—C22—P2 | 104.2 (2) |
C4—C5—H5A | 114.4 | C23—C22—H22A | 107.7 |
Rh1—C5—H5A | 114.4 | C21—C22—H22A | 107.7 |
C5—C6—C7 | 127.3 (4) | P2—C22—H22A | 107.7 |
C5—C6—Rh1 | 74.32 (19) | C22—C23—C24 | 114.8 (3) |
C7—C6—Rh1 | 105.8 (2) | C22—C23—H23A | 108.6 |
C5—C6—H6A | 113.7 | C24—C23—H23A | 108.6 |
C7—C6—H6A | 113.7 | C22—C23—H23B | 108.6 |
Rh1—C6—H6A | 113.7 | C24—C23—H23B | 108.6 |
C6—C7—C8 | 115.2 (4) | H23A—C23—H23B | 107.5 |
C6—C7—H7A | 108.5 | C23—C24—H24A | 109.5 |
C8—C7—H7A | 108.5 | C23—C24—H24B | 109.5 |
C6—C7—H7B | 108.5 | H24A—C24—H24B | 109.5 |
C8—C7—H7B | 108.5 | C23—C24—H24C | 109.5 |
H7A—C7—H7B | 107.5 | H24A—C24—H24C | 109.5 |
C1—C8—C7 | 113.3 (3) | H24B—C24—H24C | 109.5 |
C1—C8—H8A | 108.9 | C26—C25—C19 | 113.1 (3) |
C7—C8—H8A | 108.9 | C26—C25—H25A | 109.0 |
C1—C8—H8B | 108.9 | C19—C25—H25A | 109.0 |
C7—C8—H8B | 108.9 | C26—C25—H25B | 109.0 |
H8A—C8—H8B | 107.7 | C19—C25—H25B | 109.0 |
C10—C9—P1 | 107.57 (19) | H25A—C25—H25B | 107.8 |
C10—C9—H9A | 110.2 | C25—C26—H26A | 109.5 |
P1—C9—H9A | 110.2 | C25—C26—H26B | 109.5 |
C10—C9—H9B | 110.2 | H26A—C26—H26B | 109.5 |
P1—C9—H9B | 110.2 | C25—C26—H26C | 109.5 |
H9A—C9—H9B | 108.5 | H26A—C26—H26C | 109.5 |
C9—C10—P2 | 107.82 (19) | H26B—C26—H26C | 109.5 |
C9—C10—H10A | 110.1 | F1—B1—F2 | 119.1 (4) |
P2—C10—H10A | 110.1 | F1—B1—F4 | 89.5 (5) |
C9—C10—H10B | 110.1 | F2—B1—F4 | 114.3 (5) |
P2—C10—H10B | 110.1 | F1—B1—F3' | 99.5 (4) |
H10A—C10—H10B | 108.5 | F2—B1—F3' | 81.1 (5) |
C15—C11—C12 | 115.7 (2) | F4—B1—F3' | 155.6 (6) |
C15—C11—P1 | 115.8 (2) | F1—B1—F3 | 106.4 (4) |
C12—C11—P1 | 102.44 (19) | F2—B1—F3 | 109.9 (4) |
C15—C11—H11A | 107.5 | F4—B1—F3 | 116.4 (5) |
C12—C11—H11A | 107.5 | F1—B1—F4' | 125.4 (4) |
P1—C11—H11A | 107.5 | F2—B1—F4' | 109.1 (4) |
C13—C12—C11 | 107.6 (2) | F4—B1—F4' | 46.1 (4) |
C13—C12—H12A | 110.2 | F3'—B1—F4' | 112.3 (5) |
C11—C12—H12A | 110.2 | F3—B1—F4' | 77.7 (4) |
C13—C12—H12B | 110.2 | F1—B1—F2' | 109.4 (4) |
C11—C12—H12B | 110.2 | F4—B1—F2' | 90.9 (5) |
H12A—C12—H12B | 108.5 | F3'—B1—F2' | 107.0 (5) |
C12—C13—C14 | 110.1 (3) | F3—B1—F2' | 134.7 (4) |
C12—C13—H13A | 109.6 | F4'—B1—F2' | 102.3 (4) |
Experimental details
Crystal data | |
Chemical formula | [Rh(C8H12)(C18H36P2)]BF4 |
Mr | 612.32 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 200 |
a, b, c (Å) | 8.8374 (18), 16.218 (3), 19.946 (4) |
V (Å3) | 2858.7 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.75 |
Crystal size (mm) | 0.50 × 0.43 × 0.40 |
Data collection | |
Diffractometer | STOE IPDS 2 |
Absorption correction | Numerical (X-SHAPE; Stoe & Cie, 2005) |
Tmin, Tmax | 0.728, 0.858 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 36650, 6075, 5779 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.634 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.073, 1.06 |
No. of reflections | 6075 |
No. of parameters | 305 |
No. of restraints | 21 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.95, −0.34 |
Absolute structure | Flack (1983), 2621 Friedel pairs |
Absolute structure parameter | −0.02 (2) |
Computer programs: X-AREA (Stoe & Cie, 2005), X-RED32 (Stoe & Cie, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Acknowledgements
This work was supported by the Leibniz-Institut für Katalyse e. V. an der Universität Rostock.
References
Axtell, A. T., Cobley, C. J., Klosin, J., Whiteker, G. T., Zanotti-Gerosa, A. & Abboud, K. A. (2005). Angew. Chem. Int. Ed. 44, 5834–5838. Web of Science CSD CrossRef CAS Google Scholar
Burk, M. J., Bienewald, F., Harris, M. & Zanotti-Gerosa, A. (1998). Angew. Chem. Int. Ed. 37, 1931–1933. CrossRef CAS Google Scholar
Burk, M. J., Feaster, J. E. & Harlow, R. L. (1990). Organometallics, 9, 2653–2655. CSD CrossRef CAS Web of Science Google Scholar
Drexler, H.-J., Baumann, W., Spannenberg, A., Fischer, C. & Heller, D. (2001). J. Organomet. Chem. 621, 89–102. Web of Science CSD CrossRef CAS Google Scholar
Drexler, H.-J., Zhang, S., Sun, A., Spannenberg, A., Arrieta, A., Preetz, A. & Heller, D. (2004). Tetrahedron Asymmetry, 15, 2139–2150. Web of Science CSD CrossRef CAS Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Jerphagnon, T., Renaud, J.-L., Demonchaux, P., Ferreira, A. & Bruneau, C. (2003). Tetrahedron Asymmetry, 14, 1973–1977. Web of Science CrossRef CAS Google Scholar
Schulz, S., Drexler, H.-J. & Heller, D. (2010). Acta Cryst. E66, m721–m722. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (2005). X-AREA, X-RED32and X-SHAPE. Stoe & Cie, Darmstadt, Germany. Google Scholar
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The geometry of the cation of the title compound is comparable with the three independent complexes described in Schulz et al. (2010): the dihedral angle between the planes P1,Rh1,P2 and X1,Rh1,X2 (X = centroid of the double bond) of 14.0 (1)° corresponds to those in the Me-BPE complexes (14.7 (1)°, 14.8 (1)° and 15.3 (1)°). Furthermore, the dihedral angle is not the value found for the corresponding Et-DuPhos complex [Rh((R,R)-Et-DuPhos)COD]BF4 (21.1 (1)°) (Drexler et al., 2001) or for the complex [Rh((R,R)-Me-BPE)COD]SbF6 (19.4°) (Burk et al., 1990; Drexler et al., 2004). The cationic rhodium bisphosphine diolefine complexes build up five-membered ring chelates with rhodium (Fig. 1). For the title compound the molecular structure shows a δ-conformation of the backbone of the bisphosphine. The COD is η2,η2-coordinated and is orientated in an anticlockwise twist manner. An intramolecular P1—Rh1—P2 angle of 83.91 (2)° is obtained. This is in the same range of corresponding complexes already described in the literature Schulz et al. (2010) and literature therein. The bonds Rh1—P1 and Rh1—P2 show bond lengths of 2.2754 (8) Å and 2.2702 (8) Å, respectively. Applications of the ligand Et-BPE in catalytic reactions are reported by Axtell et al. (2005); Jerphagnon et al. (2003) and Burk et al. (1998).