metal-organic compounds
(η4-1,5-Cyclooctadiene)[(R)-(+)-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-bis(diphenylphosphanyl)-1,1′-binaphthyl-κ2P,P′]rhodium(I) tetrafluoroborate 0.72-pentane 0.56-methanol solvate
aLeibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany
*Correspondence e-mail: hans-joachim.drexler@catalysis.de
The title compound, [Rh(C8H12)(C44H20P2)]BF4·0.72C5H12·0.56·CH4O, crystallizes in the Sohncke P21. The RhI centre is coordinated by a H8-BINAP 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-bis(diphenylphosphanyl)-1,1′-binaphthyl ligand and by a bidentate η2,η2-coordinated cod (cycloocta-1,5-diene) ligand. The contains one cation, one anion and cocrystallized pentane [occupancy 0.720 (4)] and methanol [2 × 0.280 (4) occupancy] molecules. The rhodium(I) complex [Rh(H8-BINAP)(cod)]BF4 has been applied as a precatalyst in the asymmetric intramolecular [2+2+2] cycloaddition of enediynes, affording excellent enantiomeric excesses [Shibata et al. (2007). J. Org. Chem. 72, 6521–6525].
Keywords: crystal structure; rhodium complex; hydrogenation.
CCDC reference: 1531751
Structure description
One of our main interests lies in the field of homogeneous asymmetric catalysis, with a special focus on asymmetric hydrogenation promoted by chiral rhodium bisphosphine complexes. A well known chiral ligand that forms seven-membered ring chelates is BINAP (Miyashita et al., 1980).
A novel ligand, H8-BINAP, developed recently by Takaya et al., is able to coordinate to rhodium, affording a seven-membered chelate complex (Zhang et al., 1994). The structure of the cod rhodium perchlorate complex [Rh(H8-BINAP)(cod)]ClO4 containing the H8-BINAP ligand is described in this article.
The title compound, [Rh(H8-BINAP)(cod)]BF4, crystallizes in the Sohncke P21 as red prisms. This is isomorphous to the related perchlorate complex [Rh(H8-BINAP)(cod)]ClO4 (Zhang et al., 1994). The cationic complex of rhodium(I) is coordinated by a H8-BINAP ligand and by a cycloocta-1,5-diene ligand in an η2,η2 fashion (Fig. 1). The contains one cation, one anion, and cocrystallized pentane (0.72) and methanol (2 × 0.28) molecules.
The P—Rh—P bite angles is 91.055 (19)° for [Rh(H8-BINAP)(cod)]BF4 and 90.58° for [Rh(H8-BINAP)(cod)]ClO4 (Table 1), and are in the same range as those found in the parent BINAP diolefin complexes [Rh(BINAP)(diolefin)]X (with diolefin = nbd, cod; X = BF4, ClO4, OTf) 88.7 (1)–91.8 (1)° (Preetz et al., 2011, and references therein). Comparable distances, e.g. Rh—P (Table 1), are also similar. The dihedral angles between the P/Rh/P and CM/Rh/CM planes (CM = centroid of the double bond) are 1.98 (7)° for the title compound and 1.99° for the perchlorate rhodium complex. In general, this value is smaller for the rhodium H8-BINAP complexes than for the related rhodium BINAP complexes 7.5–16.8° {an exception is the [Rh(BINAP)(nbd)](OTf) complex with 0.3°} (Preetz et al., 2010).
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The application of [Rh(H8-BINAP)(cod)]BF4 as a precatalyst in the asymmetric intramolecular [2+2+2] cycloaddidion of enediynes leads to an excellent enantiomeric excesses (up to 98 ee%) (Shibata et al., 2007). Hydrogenation of the cod is necessary to obtain the active catalyst.
To determine the prehydrogenation time, catalytic hydrogenations of cod and nbd (norbornadiene) with [Rh(H8-BINAP)(cod)]BF4 or [Rh(H8-BINAP)(nbd)]BF4, respectively, have been carried out in MeOH according to Heller et al. (Drexler et al., 2007).
Pseudo-rate constants were determined from the slope of the hydrogen consumption from the linear part of the curve – which represents the hydrogenation of the first double bond of the diolefin. Fig. 2 shows the hydrogen consumption curves for the catalytic hydrogenation of the first double bond with a high excess of cod and nbd. For the hydrogenation of nbd, we found 57.5 min−1 and for cod 0.851 min−1. This gives a ratio of k′2nnbd/k′2cod of 67.6. The rate constants are slightly higher than those observed for BINAP rhodium complexes (27/0.23 min−1) (Meissner et al., 2014).
Synthesis and crystallization
All manipulations were carried out with standard Schlenk techniques under argon. NMR spectra were recorded on a Bruker ARX-300 spectrometer. Hydrogen consumptions were monitored using the device described in Drexler et al. (2007).
The cationic complexes [Rh(H8-BINAP)(cod)]BF4 and [Rh(H8-BINAP)(nbd)]BF4 were prepared by reaction of [Rh(diolefin)(acac)] and H8-BINAP followed by addition of HBF4 to the resulting solution, according to a modification of a previously published procedure (Schrock & Osborn, 1971). By overlaying a solution of [Rh(H8-BINAP)(cod)]BF4 in methanol with pentane, red single crystals suitable for X-ray analysis were obtained.
31P NMR (MeOH-d4, 298 K, 121 MHz): [Rh(H8-BINAP)(cod)]BF4: δ 24.7 (d, JP-Rh = 145.8 Hz); [Rh(H8-BINAP)(nbd)]BF4: δ 25.4 (d, JP-Rh = 155.9 Hz).
Refinement
Crystal data, data collection and structure . The R for the title compound was determined using 5105 quotients in the The at convergence was −0.008 (3).
details are summarized in Table 2After 4− anion in [Rh(H8-BINAP)(cod)]BF4, residual electron density and large anisotropic displacement parameters indicated an alternative orientation for this moiety. The occupancy of the alternative orientations was refined and their sum was constrained to unity; converged for a ratio of 0.535 (8):0.465 (8) between the major and minor orientation. Restraints were used to equalize the bond lengths to improve the geometry and give similar Uij components for the disordered BF4− anion.
of the BFAtoms C6 and C7 are disordered and were split, together with their neighbouring C5 and C8 atoms, in alternative positions, with an occupancy ratio of 0.727 (5):0273 (5), and were restrained to have similar Uij components.
The solvent molecules share one position with a pentane–methanol ratio of 0.720 (4):[2 × 0.280 (4)] and were also restrained have similar Uij components. The C—O distances in the methanol molecules were restrained to target values of 1.44 Å. The C—C distances in the pentane molecules were restrained to be similar.
Structural data
CCDC reference: 1531751
https://doi.org/10.1107/S2414314617012408/pk4016sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617012408/pk4016Isup2.hkl
Data collection: APEX2 (Bruker, 2014); cell
SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).[Rh(C8H12)(C44H20P2)]BF4·0.72C5H12·0.56CH4O | F(000) = 1041 |
Mr = 998.48 | Dx = 1.385 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 11.0916 (2) Å | Cell parameters from 9769 reflections |
b = 15.3047 (3) Å | θ = 2.3–27.5° |
c = 14.1459 (3) Å | µ = 0.48 mm−1 |
β = 94.260 (1)° | T = 150 K |
V = 2394.68 (8) Å3 | Prism, red |
Z = 2 | 0.50 × 0.42 × 0.22 mm |
Bruker APEXII CCD diffractometer | 10991 independent reflections |
Radiation source: fine-focus sealed tube | 10761 reflections with I > 2σ(I) |
Detector resolution: 8.3333 pixels mm-1 | Rint = 0.029 |
φ and ω scans | θmax = 27.5°, θmin = 1.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | h = −14→14 |
Tmin = 0.686, Tmax = 0.746 | k = −19→19 |
125039 measured reflections | l = −18→18 |
Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.019 | w = 1/[σ2(Fo2) + (0.0294P)2 + 0.6009P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.049 | (Δ/σ)max = 0.001 |
S = 1.04 | Δρmax = 0.30 e Å−3 |
10991 reflections | Δρmin = −0.30 e Å−3 |
685 parameters | Absolute structure: Flack x determined using 5105 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
260 restraints | Absolute structure parameter: −0.008 (3) |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Rh1 | 0.82304 (2) | 0.75126 (2) | 0.80792 (2) | 0.01878 (4) | |
P1 | 0.74750 (5) | 0.82768 (4) | 0.67490 (4) | 0.01918 (10) | |
P2 | 0.84440 (5) | 0.88047 (3) | 0.89523 (4) | 0.01791 (10) | |
C1 | 0.64594 (19) | 0.91929 (14) | 0.69716 (15) | 0.0201 (4) | |
C2 | 0.5207 (2) | 0.90898 (16) | 0.68133 (17) | 0.0264 (5) | |
H2 | 0.4892 | 0.8607 | 0.6452 | 0.032* | |
C3 | 0.4425 (2) | 0.96830 (17) | 0.71766 (18) | 0.0291 (5) | |
H3 | 0.3579 | 0.9594 | 0.7069 | 0.035* | |
C4 | 0.4843 (2) | 1.04049 (16) | 0.76942 (16) | 0.0244 (4) | |
C5 | 0.3906 (8) | 1.0986 (9) | 0.8093 (15) | 0.0285 (16) | 0.720 (4) |
H5A | 0.3654 | 1.0730 | 0.8690 | 0.034* | 0.720 (4) |
H5B | 0.3185 | 1.1019 | 0.7638 | 0.034* | 0.720 (4) |
C6 | 0.4394 (3) | 1.1894 (3) | 0.8284 (3) | 0.0334 (8) | 0.720 (4) |
H6A | 0.3815 | 1.2236 | 0.8635 | 0.040* | 0.720 (4) |
H6B | 0.4501 | 1.2196 | 0.7677 | 0.040* | 0.720 (4) |
C7 | 0.5611 (3) | 1.1837 (2) | 0.8869 (3) | 0.0326 (7) | 0.720 (4) |
H7A | 0.5893 | 1.2433 | 0.9044 | 0.039* | 0.720 (4) |
H7B | 0.5506 | 1.1510 | 0.9461 | 0.039* | 0.720 (4) |
C8 | 0.6557 (2) | 1.13826 (16) | 0.83163 (17) | 0.0271 (5) | 0.720 (4) |
H8A | 0.6845 | 1.1795 | 0.7843 | 0.033* | 0.720 (4) |
H8B | 0.7258 | 1.1226 | 0.8759 | 0.033* | 0.720 (4) |
C5B | 0.402 (2) | 1.102 (2) | 0.820 (4) | 0.0285 (16) | 0.280 (4) |
H5C | 0.3407 | 1.1246 | 0.7713 | 0.034* | 0.280 (4) |
H5D | 0.3581 | 1.0665 | 0.8644 | 0.034* | 0.280 (4) |
C6B | 0.4524 (9) | 1.1816 (7) | 0.8755 (8) | 0.0334 (8) | 0.280 (4) |
H6C | 0.3902 | 1.2279 | 0.8756 | 0.040* | 0.280 (4) |
H6D | 0.4754 | 1.1647 | 0.9419 | 0.040* | 0.280 (4) |
C7B | 0.5621 (8) | 1.2150 (6) | 0.8290 (7) | 0.0326 (7) | 0.280 (4) |
H7C | 0.5970 | 1.2662 | 0.8639 | 0.039* | 0.280 (4) |
H7D | 0.5394 | 1.2326 | 0.7627 | 0.039* | 0.280 (4) |
C8B | 0.6557 (2) | 1.13826 (16) | 0.83163 (17) | 0.0271 (5) | 0.280 (4) |
H8C | 0.7291 | 1.1583 | 0.8022 | 0.033* | 0.280 (4) |
H8D | 0.6796 | 1.1236 | 0.8986 | 0.033* | 0.280 (4) |
C9 | 0.60854 (19) | 1.05614 (14) | 0.78088 (15) | 0.0207 (4) | |
C10 | 0.68938 (19) | 0.99491 (14) | 0.74490 (15) | 0.0196 (4) | |
C11 | 0.82155 (18) | 1.01648 (14) | 0.75959 (15) | 0.0191 (4) | |
C12 | 0.86869 (19) | 1.08103 (14) | 0.70159 (15) | 0.0217 (4) | |
C13 | 0.7911 (2) | 1.11869 (16) | 0.61848 (16) | 0.0263 (4) | |
H13A | 0.7300 | 1.1581 | 0.6432 | 0.032* | |
H13B | 0.7472 | 1.0703 | 0.5846 | 0.032* | |
C14 | 0.8620 (2) | 1.16937 (18) | 0.54775 (18) | 0.0331 (5) | |
H14A | 0.9050 | 1.1278 | 0.5085 | 0.040* | |
H14B | 0.8053 | 1.2037 | 0.5051 | 0.040* | |
C15 | 0.9530 (2) | 1.23048 (15) | 0.5990 (2) | 0.0332 (6) | |
H15A | 0.9106 | 1.2715 | 0.6393 | 0.040* | |
H15B | 0.9950 | 1.2650 | 0.5523 | 0.040* | |
C16 | 1.0447 (2) | 1.17733 (17) | 0.6602 (2) | 0.0321 (5) | |
H16A | 1.0979 | 1.1457 | 0.6186 | 0.039* | |
H16B | 1.0959 | 1.2176 | 0.7006 | 0.039* | |
C17 | 0.9862 (2) | 1.11201 (15) | 0.72283 (17) | 0.0253 (4) | |
C18 | 1.0511 (2) | 1.08231 (17) | 0.80484 (19) | 0.0296 (5) | |
H18 | 1.1274 | 1.1078 | 0.8233 | 0.036* | |
C19 | 1.0069 (2) | 1.01666 (16) | 0.85966 (17) | 0.0262 (4) | |
H19 | 1.0540 | 0.9963 | 0.9141 | 0.031* | |
C20 | 0.89329 (18) | 0.97999 (14) | 0.83567 (15) | 0.0197 (4) | |
C21 | 0.66148 (18) | 0.75831 (19) | 0.58804 (14) | 0.0239 (4) | |
C22 | 0.7066 (2) | 0.73540 (17) | 0.50185 (16) | 0.0307 (6) | |
H22 | 0.7801 | 0.7604 | 0.4842 | 0.037* | |
C23 | 0.6440 (3) | 0.6759 (2) | 0.44154 (19) | 0.0396 (6) | |
H23 | 0.6761 | 0.6598 | 0.3836 | 0.047* | |
C24 | 0.5358 (3) | 0.6400 (2) | 0.4653 (2) | 0.0429 (7) | |
H24 | 0.4927 | 0.6007 | 0.4233 | 0.051* | |
C25 | 0.4909 (2) | 0.66176 (19) | 0.5506 (2) | 0.0352 (6) | |
H25 | 0.4163 | 0.6377 | 0.5670 | 0.042* | |
C26 | 0.5540 (2) | 0.71860 (17) | 0.61255 (18) | 0.0287 (5) | |
H26 | 0.5241 | 0.7308 | 0.6724 | 0.034* | |
C27 | 0.8710 (2) | 0.87183 (15) | 0.61120 (17) | 0.0270 (5) | |
C28 | 0.9896 (2) | 0.85627 (18) | 0.64660 (19) | 0.0346 (6) | |
H28 | 1.0053 | 0.8213 | 0.7016 | 0.041* | |
C29 | 1.0854 (3) | 0.8923 (2) | 0.6008 (3) | 0.0503 (9) | |
H29 | 1.1663 | 0.8828 | 0.6257 | 0.060* | |
C30 | 1.0637 (4) | 0.9411 (2) | 0.5207 (3) | 0.0601 (11) | |
H30 | 1.1293 | 0.9658 | 0.4904 | 0.072* | |
C31 | 0.9461 (4) | 0.95470 (19) | 0.4834 (2) | 0.0523 (9) | |
H31 | 0.9316 | 0.9876 | 0.4268 | 0.063* | |
C32 | 0.8490 (3) | 0.92039 (17) | 0.52838 (19) | 0.0369 (6) | |
H32 | 0.7684 | 0.9300 | 0.5028 | 0.044* | |
C33 | 0.9548 (2) | 0.86850 (14) | 0.99747 (16) | 0.0221 (4) | |
C34 | 0.9212 (2) | 0.86878 (15) | 1.09020 (17) | 0.0263 (4) | |
H34 | 0.8395 | 0.8800 | 1.1024 | 0.032* | |
C35 | 1.0070 (3) | 0.85256 (17) | 1.16552 (18) | 0.0345 (6) | |
H35 | 0.9835 | 0.8529 | 1.2287 | 0.041* | |
C36 | 1.1260 (3) | 0.83602 (18) | 1.1485 (2) | 0.0384 (6) | |
H36 | 1.1842 | 0.8255 | 1.1999 | 0.046* | |
C37 | 1.1599 (2) | 0.83480 (18) | 1.0566 (2) | 0.0356 (6) | |
H37 | 1.2416 | 0.8232 | 1.0450 | 0.043* | |
C38 | 1.0753 (2) | 0.85041 (16) | 0.98093 (18) | 0.0285 (5) | |
H38 | 1.0993 | 0.8488 | 0.9179 | 0.034* | |
C39 | 0.7030 (2) | 0.90642 (15) | 0.94537 (16) | 0.0206 (4) | |
C40 | 0.6040 (2) | 0.85126 (15) | 0.92366 (15) | 0.0226 (4) | |
H40 | 0.6122 | 0.8022 | 0.8835 | 0.027* | |
C41 | 0.4933 (2) | 0.86829 (17) | 0.96094 (18) | 0.0289 (5) | |
H41 | 0.4257 | 0.8315 | 0.9454 | 0.035* | |
C42 | 0.4827 (2) | 0.93896 (18) | 1.02050 (19) | 0.0333 (5) | |
H42 | 0.4079 | 0.9497 | 1.0470 | 0.040* | |
C43 | 0.5796 (2) | 0.99438 (17) | 1.04220 (18) | 0.0317 (5) | |
H43 | 0.5710 | 1.0429 | 1.0830 | 0.038* | |
C44 | 0.6896 (2) | 0.97870 (16) | 1.00391 (16) | 0.0256 (4) | |
H44 | 0.7557 | 1.0173 | 1.0176 | 0.031* | |
C45 | 0.8571 (3) | 0.63513 (16) | 0.71861 (17) | 0.0312 (5) | |
H45 | 0.854 (3) | 0.658 (2) | 0.6563 (13) | 0.037* | |
C46 | 0.7485 (2) | 0.62307 (16) | 0.75734 (17) | 0.0289 (5) | |
H46 | 0.6797 (19) | 0.638 (2) | 0.7163 (19) | 0.035* | |
C47 | 0.7242 (3) | 0.56199 (17) | 0.83809 (19) | 0.0341 (5) | |
H47A | 0.7828 | 0.5131 | 0.8394 | 0.041* | |
H47B | 0.6421 | 0.5371 | 0.8266 | 0.041* | |
C48 | 0.7341 (3) | 0.60797 (18) | 0.9345 (2) | 0.0343 (6) | |
H48A | 0.6557 | 0.6359 | 0.9448 | 0.041* | |
H48B | 0.7503 | 0.5637 | 0.9849 | 0.041* | |
C49 | 0.8322 (2) | 0.67644 (16) | 0.94369 (16) | 0.0286 (5) | |
H49 | 0.825 (3) | 0.7198 (16) | 0.9912 (17) | 0.034* | |
C50 | 0.9438 (2) | 0.66987 (16) | 0.90917 (18) | 0.0298 (5) | |
H50 | 1.002 (2) | 0.7099 (17) | 0.933 (2) | 0.036* | |
C51 | 0.9928 (3) | 0.59022 (19) | 0.8617 (2) | 0.0389 (6) | |
H51A | 0.9510 | 0.5375 | 0.8834 | 0.047* | |
H51B | 1.0799 | 0.5842 | 0.8812 | 0.047* | |
C52 | 0.9760 (3) | 0.5953 (2) | 0.7534 (2) | 0.0419 (7) | |
H52A | 1.0424 | 0.6304 | 0.7298 | 0.050* | |
H52B | 0.9814 | 0.5357 | 0.7269 | 0.050* | |
B1 | 0.3031 (12) | 0.7140 (7) | 0.7996 (7) | 0.057 (3) | 0.465 (8) |
F1 | 0.4258 (13) | 0.7105 (12) | 0.8181 (14) | 0.067 (4) | 0.465 (8) |
F2 | 0.2657 (7) | 0.6820 (9) | 0.7125 (6) | 0.110 (3) | 0.465 (8) |
F3 | 0.2551 (10) | 0.6727 (7) | 0.8737 (9) | 0.097 (3) | 0.465 (8) |
F4 | 0.2698 (7) | 0.8003 (5) | 0.8041 (7) | 0.094 (3) | 0.465 (8) |
B1' | 0.3170 (10) | 0.6974 (6) | 0.7955 (6) | 0.050 (2) | 0.535 (8) |
F1' | 0.4392 (10) | 0.6892 (9) | 0.8172 (10) | 0.052 (2) | 0.535 (8) |
F2' | 0.2769 (4) | 0.6183 (4) | 0.7588 (6) | 0.087 (2) | 0.535 (8) |
F3' | 0.2536 (10) | 0.7148 (7) | 0.8722 (8) | 0.106 (3) | 0.535 (8) |
F4' | 0.2971 (5) | 0.7590 (7) | 0.7271 (7) | 0.118 (3) | 0.535 (8) |
O71 | 0.4066 (17) | 0.9398 (14) | 0.4145 (13) | 0.126 (7) | 0.280 (4) |
H71 | 0.3902 | 0.9265 | 0.4697 | 0.189* | 0.280 (4) |
C71 | 0.3348 (19) | 0.889 (2) | 0.348 (2) | 0.114 (10) | 0.280 (4) |
H71A | 0.3770 | 0.8824 | 0.2904 | 0.171* | 0.280 (4) |
H71B | 0.2574 | 0.9189 | 0.3334 | 0.171* | 0.280 (4) |
H71C | 0.3203 | 0.8317 | 0.3756 | 0.171* | 0.280 (4) |
O61 | 0.7249 (11) | 0.9616 (14) | 0.2888 (11) | 0.100 (4) | 0.280 (4) |
H61 | 0.7470 | 1.0119 | 0.2735 | 0.150* | 0.280 (4) |
C61 | 0.5993 (7) | 0.9633 (4) | 0.3056 (4) | 0.1080 (19) | 0.280 (4) |
H61A | 0.5701 | 1.0238 | 0.3028 | 0.162* | 0.280 (4) |
H61B | 0.5883 | 0.9389 | 0.3684 | 0.162* | 0.280 (4) |
H61C | 0.5534 | 0.9285 | 0.2572 | 0.162* | 0.280 (4) |
C73 | 0.6896 (10) | 0.9051 (6) | 0.2781 (6) | 0.098 (3) | 0.720 (4) |
H73A | 0.7356 | 0.9330 | 0.2298 | 0.148* | 0.720 (4) |
H73B | 0.6515 | 0.8517 | 0.2520 | 0.148* | 0.720 (4) |
H73C | 0.7443 | 0.8904 | 0.3334 | 0.148* | 0.720 (4) |
C74 | 0.5993 (7) | 0.9633 (4) | 0.3056 (4) | 0.1080 (19) | 0.720 (4) |
H74A | 0.6377 | 1.0158 | 0.3355 | 0.130* | 0.720 (4) |
H74B | 0.5481 | 0.9822 | 0.2490 | 0.130* | 0.720 (4) |
C75 | 0.5288 (9) | 0.9228 (8) | 0.3685 (10) | 0.154 (4) | 0.720 (4) |
H75A | 0.5337 | 0.9579 | 0.4275 | 0.184* | 0.720 (4) |
H75B | 0.5659 | 0.8653 | 0.3845 | 0.184* | 0.720 (4) |
C76 | 0.3983 (12) | 0.9077 (13) | 0.3401 (13) | 0.170 (5) | 0.720 (4) |
H76A | 0.3555 | 0.9633 | 0.3246 | 0.204* | 0.720 (4) |
H76B | 0.3874 | 0.8676 | 0.2852 | 0.204* | 0.720 (4) |
C77 | 0.3581 (8) | 0.8689 (7) | 0.4240 (8) | 0.110 (3) | 0.720 (4) |
H77A | 0.2748 | 0.8483 | 0.4116 | 0.164* | 0.720 (4) |
H77B | 0.3613 | 0.9124 | 0.4750 | 0.164* | 0.720 (4) |
H77C | 0.4106 | 0.8195 | 0.4431 | 0.164* | 0.720 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Rh1 | 0.01974 (7) | 0.01788 (7) | 0.01896 (7) | −0.00079 (7) | 0.00298 (5) | −0.00042 (7) |
P1 | 0.0202 (2) | 0.0204 (2) | 0.0174 (2) | −0.00308 (19) | 0.00387 (19) | −0.00066 (19) |
P2 | 0.0161 (2) | 0.0194 (2) | 0.0184 (2) | −0.00075 (19) | 0.00228 (18) | −0.00018 (19) |
C1 | 0.0196 (9) | 0.0221 (10) | 0.0186 (9) | 0.0001 (8) | 0.0020 (7) | 0.0026 (8) |
C2 | 0.0226 (10) | 0.0240 (11) | 0.0319 (12) | −0.0017 (8) | −0.0031 (9) | 0.0006 (9) |
C3 | 0.0144 (9) | 0.0334 (12) | 0.0386 (13) | −0.0011 (9) | −0.0033 (9) | 0.0045 (10) |
C4 | 0.0204 (10) | 0.0286 (11) | 0.0242 (10) | 0.0033 (8) | 0.0028 (8) | 0.0080 (8) |
C5 | 0.018 (2) | 0.0358 (18) | 0.031 (5) | 0.0054 (16) | 0.003 (3) | 0.0032 (14) |
C6 | 0.0302 (16) | 0.0332 (16) | 0.037 (2) | 0.0115 (12) | 0.0025 (18) | −0.0035 (18) |
C7 | 0.0295 (15) | 0.0326 (17) | 0.0357 (18) | 0.0058 (13) | 0.0024 (14) | −0.0112 (13) |
C8 | 0.0239 (10) | 0.0273 (11) | 0.0302 (11) | 0.0020 (9) | 0.0023 (9) | −0.0049 (9) |
C5B | 0.018 (2) | 0.0358 (18) | 0.031 (5) | 0.0054 (16) | 0.003 (3) | 0.0032 (14) |
C6B | 0.0302 (16) | 0.0332 (16) | 0.037 (2) | 0.0115 (12) | 0.0025 (18) | −0.0035 (18) |
C7B | 0.0295 (15) | 0.0326 (17) | 0.0357 (18) | 0.0058 (13) | 0.0024 (14) | −0.0112 (13) |
C8B | 0.0239 (10) | 0.0273 (11) | 0.0302 (11) | 0.0020 (9) | 0.0023 (9) | −0.0049 (9) |
C9 | 0.0200 (10) | 0.0227 (10) | 0.0196 (9) | 0.0008 (8) | 0.0020 (7) | 0.0046 (8) |
C10 | 0.0180 (9) | 0.0225 (10) | 0.0182 (9) | −0.0014 (8) | 0.0012 (7) | 0.0036 (7) |
C11 | 0.0164 (9) | 0.0193 (9) | 0.0221 (10) | −0.0019 (7) | 0.0042 (7) | −0.0025 (8) |
C12 | 0.0209 (10) | 0.0212 (10) | 0.0234 (10) | −0.0003 (8) | 0.0044 (8) | 0.0008 (8) |
C13 | 0.0261 (11) | 0.0258 (11) | 0.0269 (11) | −0.0031 (9) | 0.0014 (8) | 0.0052 (9) |
C14 | 0.0393 (13) | 0.0318 (13) | 0.0287 (12) | −0.0035 (11) | 0.0055 (10) | 0.0048 (10) |
C15 | 0.0349 (12) | 0.0269 (14) | 0.0384 (13) | −0.0056 (9) | 0.0066 (10) | 0.0087 (9) |
C16 | 0.0258 (11) | 0.0279 (12) | 0.0438 (14) | −0.0053 (9) | 0.0096 (10) | 0.0087 (10) |
C17 | 0.0199 (10) | 0.0222 (10) | 0.0346 (12) | −0.0016 (8) | 0.0078 (8) | 0.0039 (9) |
C18 | 0.0179 (10) | 0.0297 (12) | 0.0409 (13) | −0.0056 (9) | 0.0001 (9) | 0.0032 (10) |
C19 | 0.0199 (10) | 0.0272 (11) | 0.0310 (11) | −0.0015 (8) | −0.0018 (8) | 0.0021 (9) |
C20 | 0.0174 (9) | 0.0196 (10) | 0.0226 (10) | −0.0015 (7) | 0.0042 (7) | −0.0006 (8) |
C21 | 0.0259 (9) | 0.0249 (11) | 0.0205 (8) | −0.0011 (11) | −0.0009 (7) | −0.0010 (10) |
C22 | 0.0311 (11) | 0.0378 (17) | 0.0233 (10) | −0.0029 (10) | 0.0019 (8) | −0.0058 (9) |
C23 | 0.0396 (14) | 0.0521 (17) | 0.0265 (12) | −0.0009 (13) | −0.0008 (10) | −0.0148 (12) |
C24 | 0.0384 (14) | 0.0485 (17) | 0.0400 (15) | −0.0066 (13) | −0.0091 (11) | −0.0178 (13) |
C25 | 0.0267 (12) | 0.0375 (14) | 0.0406 (14) | −0.0063 (10) | −0.0038 (10) | −0.0061 (11) |
C26 | 0.0285 (12) | 0.0293 (11) | 0.0285 (11) | −0.0054 (9) | 0.0043 (9) | −0.0056 (9) |
C27 | 0.0310 (11) | 0.0259 (11) | 0.0259 (11) | −0.0082 (9) | 0.0134 (9) | −0.0062 (9) |
C28 | 0.0295 (12) | 0.0378 (14) | 0.0381 (13) | −0.0101 (10) | 0.0141 (10) | −0.0135 (11) |
C29 | 0.0358 (15) | 0.0528 (18) | 0.066 (2) | −0.0217 (14) | 0.0280 (14) | −0.0252 (16) |
C30 | 0.069 (2) | 0.0457 (18) | 0.073 (2) | −0.0285 (17) | 0.053 (2) | −0.0211 (17) |
C31 | 0.090 (3) | 0.0296 (14) | 0.0422 (16) | −0.0148 (15) | 0.0405 (17) | −0.0056 (12) |
C32 | 0.0573 (17) | 0.0269 (12) | 0.0291 (12) | −0.0066 (11) | 0.0202 (12) | −0.0013 (10) |
C33 | 0.0231 (10) | 0.0182 (10) | 0.0242 (10) | −0.0018 (8) | −0.0037 (8) | 0.0000 (8) |
C34 | 0.0301 (11) | 0.0222 (11) | 0.0261 (11) | −0.0003 (9) | −0.0012 (9) | 0.0020 (8) |
C35 | 0.0480 (15) | 0.0289 (12) | 0.0250 (12) | 0.0011 (11) | −0.0076 (10) | 0.0044 (10) |
C36 | 0.0403 (14) | 0.0304 (13) | 0.0412 (15) | −0.0016 (11) | −0.0182 (11) | 0.0087 (11) |
C37 | 0.0244 (11) | 0.0301 (13) | 0.0506 (16) | 0.0005 (10) | −0.0079 (10) | 0.0063 (11) |
C38 | 0.0241 (11) | 0.0257 (11) | 0.0352 (12) | −0.0011 (9) | −0.0005 (9) | 0.0023 (9) |
C39 | 0.0198 (10) | 0.0245 (11) | 0.0178 (10) | 0.0016 (8) | 0.0038 (8) | 0.0042 (8) |
C40 | 0.0220 (10) | 0.0238 (10) | 0.0226 (10) | 0.0004 (8) | 0.0059 (8) | 0.0026 (8) |
C41 | 0.0230 (11) | 0.0325 (12) | 0.0322 (12) | 0.0003 (9) | 0.0083 (9) | 0.0044 (10) |
C42 | 0.0282 (12) | 0.0390 (13) | 0.0345 (13) | 0.0092 (10) | 0.0146 (10) | 0.0035 (11) |
C43 | 0.0372 (13) | 0.0319 (12) | 0.0269 (12) | 0.0097 (10) | 0.0092 (10) | −0.0014 (9) |
C44 | 0.0277 (11) | 0.0266 (11) | 0.0228 (10) | 0.0027 (9) | 0.0030 (8) | 0.0003 (9) |
C45 | 0.0477 (15) | 0.0218 (11) | 0.0244 (11) | 0.0043 (10) | 0.0057 (10) | −0.0028 (9) |
C46 | 0.0373 (13) | 0.0212 (11) | 0.0273 (11) | −0.0043 (9) | −0.0034 (9) | −0.0027 (9) |
C47 | 0.0416 (14) | 0.0250 (12) | 0.0354 (13) | −0.0091 (10) | −0.0002 (11) | 0.0028 (10) |
C48 | 0.0447 (16) | 0.0283 (13) | 0.0301 (13) | −0.0053 (11) | 0.0044 (11) | 0.0066 (10) |
C49 | 0.0414 (13) | 0.0225 (11) | 0.0216 (11) | −0.0009 (10) | 0.0006 (9) | 0.0014 (9) |
C50 | 0.0325 (12) | 0.0217 (11) | 0.0338 (12) | 0.0002 (9) | −0.0075 (10) | 0.0005 (9) |
C51 | 0.0366 (14) | 0.0298 (13) | 0.0496 (16) | 0.0107 (11) | −0.0016 (12) | 0.0003 (11) |
C52 | 0.0438 (15) | 0.0362 (14) | 0.0473 (16) | 0.0141 (12) | 0.0145 (13) | −0.0012 (12) |
B1 | 0.038 (5) | 0.061 (5) | 0.075 (6) | −0.012 (4) | 0.011 (5) | −0.015 (5) |
F1 | 0.045 (5) | 0.083 (9) | 0.076 (5) | −0.007 (4) | 0.020 (4) | −0.033 (5) |
F2 | 0.087 (4) | 0.156 (9) | 0.084 (5) | 0.009 (5) | −0.016 (4) | −0.050 (5) |
F3 | 0.068 (4) | 0.111 (7) | 0.117 (6) | −0.009 (5) | 0.032 (4) | 0.050 (6) |
F4 | 0.081 (5) | 0.089 (5) | 0.111 (6) | 0.004 (4) | −0.001 (4) | 0.009 (4) |
B1' | 0.040 (4) | 0.049 (4) | 0.062 (4) | 0.003 (3) | 0.013 (4) | −0.003 (3) |
F1' | 0.036 (3) | 0.069 (6) | 0.052 (4) | −0.002 (3) | 0.013 (2) | 0.005 (4) |
F2' | 0.050 (3) | 0.078 (4) | 0.133 (5) | −0.009 (2) | 0.006 (3) | −0.040 (4) |
F3' | 0.078 (4) | 0.132 (7) | 0.117 (5) | −0.013 (5) | 0.062 (4) | −0.054 (5) |
F4' | 0.076 (3) | 0.119 (6) | 0.157 (7) | 0.014 (4) | −0.004 (4) | 0.058 (6) |
O71 | 0.138 (16) | 0.152 (18) | 0.090 (11) | −0.023 (13) | 0.016 (10) | −0.034 (11) |
C71 | 0.056 (11) | 0.16 (3) | 0.115 (18) | 0.014 (14) | −0.047 (12) | 0.002 (19) |
O61 | 0.104 (9) | 0.124 (11) | 0.070 (7) | 0.011 (9) | −0.006 (7) | 0.008 (9) |
C61 | 0.155 (5) | 0.088 (4) | 0.087 (4) | 0.022 (4) | 0.046 (4) | 0.019 (3) |
C73 | 0.160 (8) | 0.077 (5) | 0.058 (4) | 0.017 (5) | 0.008 (5) | 0.000 (4) |
C74 | 0.155 (5) | 0.088 (4) | 0.087 (4) | 0.022 (4) | 0.046 (4) | 0.019 (3) |
C75 | 0.129 (7) | 0.125 (7) | 0.207 (9) | 0.004 (6) | 0.013 (7) | 0.035 (7) |
C76 | 0.152 (10) | 0.155 (10) | 0.194 (11) | −0.025 (9) | −0.048 (10) | 0.055 (9) |
C77 | 0.080 (5) | 0.096 (6) | 0.150 (9) | 0.003 (5) | −0.011 (6) | 0.019 (6) |
Rh1—C46 | 2.226 (2) | C29—C30 | 1.364 (6) |
Rh1—C45 | 2.229 (2) | C29—H29 | 0.9500 |
Rh1—C49 | 2.232 (2) | C30—C31 | 1.386 (6) |
Rh1—C50 | 2.261 (2) | C30—H30 | 0.9500 |
Rh1—P1 | 2.3187 (6) | C31—C32 | 1.394 (4) |
Rh1—P2 | 2.3343 (6) | C31—H31 | 0.9500 |
P1—C27 | 1.824 (2) | C32—H32 | 0.9500 |
P1—C21 | 1.837 (2) | C33—C34 | 1.390 (3) |
P1—C1 | 1.840 (2) | C33—C38 | 1.402 (3) |
P2—C39 | 1.812 (2) | C34—C35 | 1.398 (3) |
P2—C33 | 1.833 (2) | C34—H34 | 0.9500 |
P2—C20 | 1.842 (2) | C35—C36 | 1.382 (4) |
C1—C2 | 1.399 (3) | C35—H35 | 0.9500 |
C1—C10 | 1.407 (3) | C36—C37 | 1.379 (4) |
C2—C3 | 1.381 (3) | C36—H36 | 0.9500 |
C2—H2 | 0.9500 | C37—C38 | 1.391 (4) |
C3—C4 | 1.386 (4) | C37—H37 | 0.9500 |
C3—H3 | 0.9500 | C38—H38 | 0.9500 |
C4—C9 | 1.397 (3) | C39—C44 | 1.396 (3) |
C4—C5 | 1.509 (8) | C39—C40 | 1.401 (3) |
C4—C5B | 1.53 (2) | C40—C41 | 1.396 (3) |
C5—C6 | 1.509 (11) | C40—H40 | 0.9500 |
C5—H5A | 0.9900 | C41—C42 | 1.381 (4) |
C5—H5B | 0.9900 | C41—H41 | 0.9500 |
C6—C7 | 1.532 (5) | C42—C43 | 1.386 (4) |
C6—H6A | 0.9900 | C42—H42 | 0.9500 |
C6—H6B | 0.9900 | C43—C44 | 1.392 (3) |
C7—C8 | 1.523 (4) | C43—H43 | 0.9500 |
C7—H7A | 0.9900 | C44—H44 | 0.9500 |
C7—H7B | 0.9900 | C45—C46 | 1.372 (4) |
C8—C9 | 1.521 (3) | C45—C52 | 1.503 (4) |
C8—H8A | 0.9900 | C45—H45 | 0.946 (14) |
C8—H8B | 0.9900 | C46—C47 | 1.516 (3) |
C5B—C6B | 1.53 (2) | C46—H46 | 0.953 (13) |
C5B—H5C | 0.9900 | C47—C48 | 1.532 (4) |
C5B—H5D | 0.9900 | C47—H47A | 0.9900 |
C6B—C7B | 1.514 (13) | C47—H47B | 0.9900 |
C6B—H6C | 0.9900 | C48—C49 | 1.509 (4) |
C6B—H6D | 0.9900 | C48—H48A | 0.9900 |
C7B—H7C | 0.9900 | C48—H48B | 0.9900 |
C7B—H7D | 0.9900 | C49—C50 | 1.368 (4) |
C9—C10 | 1.417 (3) | C49—H49 | 0.952 (14) |
C10—C11 | 1.502 (3) | C50—C51 | 1.512 (4) |
C11—C20 | 1.406 (3) | C50—H50 | 0.939 (14) |
C11—C12 | 1.409 (3) | C51—C52 | 1.531 (4) |
C12—C17 | 1.398 (3) | C51—H51A | 0.9900 |
C12—C13 | 1.518 (3) | C51—H51B | 0.9900 |
C13—C14 | 1.529 (3) | C52—H52A | 0.9900 |
C13—H13A | 0.9900 | C52—H52B | 0.9900 |
C13—H13B | 0.9900 | B1—F2 | 1.362 (9) |
C14—C15 | 1.520 (4) | B1—F3 | 1.366 (9) |
C14—H14A | 0.9900 | B1—F1 | 1.368 (9) |
C14—H14B | 0.9900 | B1—F4 | 1.375 (9) |
C15—C16 | 1.522 (4) | B1'—F4' | 1.357 (8) |
C15—H15A | 0.9900 | B1'—F3' | 1.362 (8) |
C15—H15B | 0.9900 | B1'—F1' | 1.374 (8) |
C16—C17 | 1.514 (3) | B1'—F2' | 1.377 (9) |
C16—H16A | 0.9900 | O71—C71 | 1.411 (13) |
C16—H16B | 0.9900 | O71—H71 | 0.8400 |
C17—C18 | 1.395 (4) | C71—H71A | 0.9800 |
C18—C19 | 1.381 (3) | C71—H71B | 0.9800 |
C18—H18 | 0.9500 | C71—H71C | 0.9800 |
C19—C20 | 1.398 (3) | O61—C61 | 1.431 (11) |
C19—H19 | 0.9500 | O61—H61 | 0.8400 |
C21—C22 | 1.397 (3) | C61—H61A | 0.9800 |
C21—C26 | 1.405 (3) | C61—H61B | 0.9800 |
C22—C23 | 1.397 (4) | C61—H61C | 0.9800 |
C22—H22 | 0.9500 | C73—H73A | 0.9800 |
C23—C24 | 1.384 (4) | C73—H73B | 0.9800 |
C23—H23 | 0.9500 | C73—H73C | 0.9800 |
C24—C25 | 1.380 (4) | C75—C76 | 1.491 (15) |
C24—H24 | 0.9500 | C75—H75A | 0.9900 |
C25—C26 | 1.387 (4) | C75—H75B | 0.9900 |
C25—H25 | 0.9500 | C76—C77 | 1.428 (15) |
C26—H26 | 0.9500 | C76—H76A | 0.9900 |
C27—C28 | 1.392 (4) | C76—H76B | 0.9900 |
C27—C32 | 1.394 (4) | C77—H77A | 0.9800 |
C28—C29 | 1.399 (4) | C77—H77B | 0.9800 |
C28—H28 | 0.9500 | C77—H77C | 0.9800 |
C46—Rh1—C45 | 35.86 (10) | C28—C27—C32 | 119.7 (2) |
C46—Rh1—C49 | 79.42 (9) | C28—C27—P1 | 118.86 (19) |
C45—Rh1—C49 | 94.58 (9) | C32—C27—P1 | 121.4 (2) |
C46—Rh1—C50 | 84.63 (9) | C27—C28—C29 | 119.7 (3) |
C45—Rh1—C50 | 78.61 (9) | C27—C28—H28 | 120.1 |
C49—Rh1—C50 | 35.44 (10) | C29—C28—H28 | 120.1 |
C46—Rh1—P1 | 94.63 (7) | C30—C29—C28 | 120.5 (3) |
C45—Rh1—P1 | 90.48 (7) | C30—C29—H29 | 119.8 |
C49—Rh1—P1 | 161.39 (7) | C28—C29—H29 | 119.8 |
C50—Rh1—P1 | 162.43 (7) | C29—C30—C31 | 120.1 (3) |
C46—Rh1—P2 | 159.61 (7) | C29—C30—H30 | 119.9 |
C45—Rh1—P2 | 163.86 (7) | C31—C30—H30 | 119.9 |
C49—Rh1—P2 | 89.02 (6) | C30—C31—C32 | 120.5 (3) |
C50—Rh1—P2 | 95.71 (7) | C30—C31—H31 | 119.8 |
P1—Rh1—P2 | 91.055 (19) | C32—C31—H31 | 119.8 |
C27—P1—C21 | 104.80 (10) | C27—C32—C31 | 119.4 (3) |
C27—P1—C1 | 107.09 (10) | C27—C32—H32 | 120.3 |
C21—P1—C1 | 105.11 (11) | C31—C32—H32 | 120.3 |
C27—P1—Rh1 | 110.39 (9) | C34—C33—C38 | 118.9 (2) |
C21—P1—Rh1 | 112.94 (9) | C34—C33—P2 | 122.28 (18) |
C1—P1—Rh1 | 115.74 (7) | C38—C33—P2 | 118.50 (17) |
C39—P2—C33 | 105.05 (10) | C33—C34—C35 | 120.2 (2) |
C39—P2—C20 | 106.89 (10) | C33—C34—H34 | 119.9 |
C33—P2—C20 | 103.98 (10) | C35—C34—H34 | 119.9 |
C39—P2—Rh1 | 109.63 (8) | C36—C35—C34 | 120.3 (2) |
C33—P2—Rh1 | 111.61 (7) | C36—C35—H35 | 119.8 |
C20—P2—Rh1 | 118.71 (7) | C34—C35—H35 | 119.8 |
C2—C1—C10 | 118.0 (2) | C37—C36—C35 | 119.8 (2) |
C2—C1—P1 | 119.98 (17) | C37—C36—H36 | 120.1 |
C10—C1—P1 | 121.11 (16) | C35—C36—H36 | 120.1 |
C3—C2—C1 | 120.6 (2) | C36—C37—C38 | 120.5 (2) |
C3—C2—H2 | 119.7 | C36—C37—H37 | 119.7 |
C1—C2—H2 | 119.7 | C38—C37—H37 | 119.7 |
C2—C3—C4 | 121.8 (2) | C37—C38—C33 | 120.2 (2) |
C2—C3—H3 | 119.1 | C37—C38—H38 | 119.9 |
C4—C3—H3 | 119.1 | C33—C38—H38 | 119.9 |
C3—C4—C9 | 119.1 (2) | C44—C39—C40 | 119.4 (2) |
C3—C4—C5 | 117.1 (4) | C44—C39—P2 | 122.61 (18) |
C9—C4—C5 | 123.8 (4) | C40—C39—P2 | 117.98 (18) |
C3—C4—C5B | 123.6 (9) | C41—C40—C39 | 120.1 (2) |
C9—C4—C5B | 117.3 (10) | C41—C40—H40 | 119.9 |
C4—C5—C6 | 111.3 (7) | C39—C40—H40 | 119.9 |
C4—C5—H5A | 109.4 | C42—C41—C40 | 119.6 (2) |
C6—C5—H5A | 109.4 | C42—C41—H41 | 120.2 |
C4—C5—H5B | 109.4 | C40—C41—H41 | 120.2 |
C6—C5—H5B | 109.4 | C41—C42—C43 | 121.0 (2) |
H5A—C5—H5B | 108.0 | C41—C42—H42 | 119.5 |
C5—C6—C7 | 109.5 (7) | C43—C42—H42 | 119.5 |
C5—C6—H6A | 109.8 | C42—C43—C44 | 119.7 (2) |
C7—C6—H6A | 109.8 | C42—C43—H43 | 120.1 |
C5—C6—H6B | 109.8 | C44—C43—H43 | 120.1 |
C7—C6—H6B | 109.8 | C43—C44—C39 | 120.2 (2) |
H6A—C6—H6B | 108.2 | C43—C44—H44 | 119.9 |
C8—C7—C6 | 111.2 (3) | C39—C44—H44 | 119.9 |
C8—C7—H7A | 109.4 | C46—C45—C52 | 126.1 (2) |
C6—C7—H7A | 109.4 | C46—C45—Rh1 | 71.96 (14) |
C8—C7—H7B | 109.4 | C52—C45—Rh1 | 108.63 (18) |
C6—C7—H7B | 109.4 | C46—C45—H45 | 117 (2) |
H7A—C7—H7B | 108.0 | C52—C45—H45 | 115 (2) |
C9—C8—C7 | 113.2 (2) | Rh1—C45—H45 | 104 (2) |
C9—C8—H8A | 108.9 | C45—C46—C47 | 126.5 (2) |
C7—C8—H8A | 108.9 | C45—C46—Rh1 | 72.18 (14) |
C9—C8—H8B | 108.9 | C47—C46—Rh1 | 112.58 (16) |
C7—C8—H8B | 108.9 | C45—C46—H46 | 114.2 (19) |
H8A—C8—H8B | 107.8 | C47—C46—H46 | 116 (2) |
C6B—C5B—C4 | 121.5 (17) | Rh1—C46—H46 | 104 (2) |
C6B—C5B—H5C | 106.9 | C46—C47—C48 | 112.5 (2) |
C4—C5B—H5C | 106.9 | C46—C47—H47A | 109.1 |
C6B—C5B—H5D | 106.9 | C48—C47—H47A | 109.1 |
C4—C5B—H5D | 106.9 | C46—C47—H47B | 109.1 |
H5C—C5B—H5D | 106.7 | C48—C47—H47B | 109.1 |
C7B—C6B—C5B | 108.7 (17) | H47A—C47—H47B | 107.8 |
C7B—C6B—H6C | 110.0 | C49—C48—C47 | 113.5 (2) |
C5B—C6B—H6C | 110.0 | C49—C48—H48A | 108.9 |
C7B—C6B—H6D | 110.0 | C47—C48—H48A | 108.9 |
C5B—C6B—H6D | 110.0 | C49—C48—H48B | 108.9 |
H6C—C6B—H6D | 108.3 | C47—C48—H48B | 108.9 |
C6B—C7B—H7C | 110.4 | H48A—C48—H48B | 107.7 |
C6B—C7B—H7D | 110.4 | C50—C49—C48 | 125.7 (2) |
H7C—C7B—H7D | 108.6 | C50—C49—Rh1 | 73.44 (14) |
C4—C9—C10 | 119.4 (2) | C48—C49—Rh1 | 107.23 (16) |
C4—C9—C8 | 119.9 (2) | C50—C49—H49 | 115.4 (19) |
C10—C9—C8 | 120.74 (19) | C48—C49—H49 | 116.6 (19) |
C1—C10—C9 | 120.87 (19) | Rh1—C49—H49 | 104.5 (19) |
C1—C10—C11 | 122.90 (19) | C49—C50—C51 | 125.6 (2) |
C9—C10—C11 | 116.23 (19) | C49—C50—Rh1 | 71.11 (14) |
C20—C11—C12 | 120.72 (19) | C51—C50—Rh1 | 112.22 (17) |
C20—C11—C10 | 120.65 (18) | C49—C50—H50 | 116 (2) |
C12—C11—C10 | 118.29 (19) | C51—C50—H50 | 115 (2) |
C17—C12—C11 | 119.5 (2) | Rh1—C50—H50 | 103 (2) |
C17—C12—C13 | 120.2 (2) | C50—C51—C52 | 112.5 (2) |
C11—C12—C13 | 120.22 (19) | C50—C51—H51A | 109.1 |
C12—C13—C14 | 114.2 (2) | C52—C51—H51A | 109.1 |
C12—C13—H13A | 108.7 | C50—C51—H51B | 109.1 |
C14—C13—H13A | 108.7 | C52—C51—H51B | 109.1 |
C12—C13—H13B | 108.7 | H51A—C51—H51B | 107.8 |
C14—C13—H13B | 108.7 | C45—C52—C51 | 112.7 (2) |
H13A—C13—H13B | 107.6 | C45—C52—H52A | 109.0 |
C15—C14—C13 | 110.8 (2) | C51—C52—H52A | 109.0 |
C15—C14—H14A | 109.5 | C45—C52—H52B | 109.0 |
C13—C14—H14A | 109.5 | C51—C52—H52B | 109.0 |
C15—C14—H14B | 109.5 | H52A—C52—H52B | 107.8 |
C13—C14—H14B | 109.5 | F2—B1—F3 | 114.7 (11) |
H14A—C14—H14B | 108.1 | F2—B1—F1 | 113.0 (13) |
C14—C15—C16 | 109.6 (2) | F3—B1—F1 | 105.9 (12) |
C14—C15—H15A | 109.8 | F2—B1—F4 | 108.8 (10) |
C16—C15—H15A | 109.8 | F3—B1—F4 | 106.7 (9) |
C14—C15—H15B | 109.8 | F1—B1—F4 | 107.2 (10) |
C16—C15—H15B | 109.8 | F4'—B1'—F3' | 111.5 (10) |
H15A—C15—H15B | 108.2 | F4'—B1'—F1' | 109.2 (9) |
C17—C16—C15 | 112.8 (2) | F3'—B1'—F1' | 113.5 (10) |
C17—C16—H16A | 109.0 | F4'—B1'—F2' | 108.1 (9) |
C15—C16—H16A | 109.0 | F3'—B1'—F2' | 107.5 (8) |
C17—C16—H16B | 109.0 | F1'—B1'—F2' | 106.9 (9) |
C15—C16—H16B | 109.0 | C71—O71—H71 | 109.5 |
H16A—C16—H16B | 107.8 | O71—C71—H71A | 109.5 |
C18—C17—C12 | 118.9 (2) | O71—C71—H71B | 109.5 |
C18—C17—C16 | 118.9 (2) | H71A—C71—H71B | 109.5 |
C12—C17—C16 | 122.1 (2) | O71—C71—H71C | 109.5 |
C19—C18—C17 | 121.4 (2) | H71A—C71—H71C | 109.5 |
C19—C18—H18 | 119.3 | H71B—C71—H71C | 109.5 |
C17—C18—H18 | 119.3 | C61—O61—H61 | 109.5 |
C18—C19—C20 | 120.5 (2) | O61—C61—H61A | 109.4 |
C18—C19—H19 | 119.8 | O61—C61—H61B | 109.4 |
C20—C19—H19 | 119.8 | H61A—C61—H61B | 109.5 |
C19—C20—C11 | 118.4 (2) | O61—C61—H61C | 109.6 |
C19—C20—P2 | 120.77 (17) | H61A—C61—H61C | 109.5 |
C11—C20—P2 | 120.64 (16) | H61B—C61—H61C | 109.5 |
C22—C21—C26 | 118.2 (2) | H73A—C73—H73B | 109.5 |
C22—C21—P1 | 121.81 (17) | H73A—C73—H73C | 109.5 |
C26—C21—P1 | 119.56 (16) | H73B—C73—H73C | 109.5 |
C21—C22—C23 | 120.2 (2) | C76—C75—H75A | 107.6 |
C21—C22—H22 | 119.9 | C76—C75—H75B | 107.6 |
C23—C22—H22 | 119.9 | H75A—C75—H75B | 107.0 |
C24—C23—C22 | 120.7 (3) | C77—C76—C75 | 101.4 (12) |
C24—C23—H23 | 119.7 | C77—C76—H76A | 111.5 |
C22—C23—H23 | 119.7 | C75—C76—H76A | 111.5 |
C25—C24—C23 | 119.5 (3) | C77—C76—H76B | 111.5 |
C25—C24—H24 | 120.2 | C75—C76—H76B | 111.5 |
C23—C24—H24 | 120.2 | H76A—C76—H76B | 109.3 |
C24—C25—C26 | 120.4 (3) | C76—C77—H77A | 109.5 |
C24—C25—H25 | 119.8 | C76—C77—H77B | 109.5 |
C26—C25—H25 | 119.8 | H77A—C77—H77B | 109.5 |
C25—C26—C21 | 120.9 (2) | C76—C77—H77C | 109.5 |
C25—C26—H26 | 119.6 | H77A—C77—H77C | 109.5 |
C21—C26—H26 | 119.6 | H77B—C77—H77C | 109.5 |
C27—P1—C1—C2 | 135.31 (19) | C27—P1—C21—C22 | 12.0 (3) |
C21—P1—C1—C2 | 24.2 (2) | C1—P1—C21—C22 | 124.7 (2) |
Rh1—P1—C1—C2 | −101.12 (18) | Rh1—P1—C21—C22 | −108.2 (2) |
C27—P1—C1—C10 | −55.60 (19) | C27—P1—C21—C26 | −175.6 (2) |
C21—P1—C1—C10 | −166.69 (17) | C1—P1—C21—C26 | −62.9 (2) |
Rh1—P1—C1—C10 | 67.97 (18) | Rh1—P1—C21—C26 | 64.2 (2) |
C10—C1—C2—C3 | −4.6 (3) | C26—C21—C22—C23 | 1.3 (4) |
P1—C1—C2—C3 | 164.83 (19) | P1—C21—C22—C23 | 173.9 (2) |
C1—C2—C3—C4 | 1.1 (4) | C21—C22—C23—C24 | 1.1 (5) |
C2—C3—C4—C9 | 3.4 (4) | C22—C23—C24—C25 | −1.6 (5) |
C2—C3—C4—C5 | −177.3 (10) | C23—C24—C25—C26 | −0.5 (5) |
C2—C3—C4—C5B | −173 (3) | C24—C25—C26—C21 | 3.0 (4) |
C3—C4—C5—C6 | −157.3 (8) | C22—C21—C26—C25 | −3.4 (4) |
C9—C4—C5—C6 | 21.9 (19) | P1—C21—C26—C25 | −176.1 (2) |
C5B—C4—C5—C6 | 50 (22) | C21—P1—C27—C28 | −122.0 (2) |
C4—C5—C6—C7 | −50.7 (15) | C1—P1—C27—C28 | 126.73 (19) |
C5—C6—C7—C8 | 64.2 (8) | Rh1—P1—C27—C28 | −0.1 (2) |
C6—C7—C8—C9 | −44.7 (4) | C21—P1—C27—C32 | 58.0 (2) |
C3—C4—C5B—C6B | −180 (3) | C1—P1—C27—C32 | −53.3 (2) |
C9—C4—C5B—C6B | 4 (6) | Rh1—P1—C27—C32 | 179.87 (18) |
C5—C4—C5B—C6B | −150 (28) | C32—C27—C28—C29 | 2.5 (4) |
C4—C5B—C6B—C7B | 32 (5) | P1—C27—C28—C29 | −177.6 (2) |
C3—C4—C9—C10 | −4.2 (3) | C27—C28—C29—C30 | −1.3 (4) |
C5—C4—C9—C10 | 176.6 (11) | C28—C29—C30—C31 | −0.6 (5) |
C5B—C4—C9—C10 | 173 (3) | C29—C30—C31—C32 | 1.4 (5) |
C3—C4—C9—C8 | 175.8 (2) | C28—C27—C32—C31 | −1.7 (4) |
C5—C4—C9—C8 | −3.3 (11) | P1—C27—C32—C31 | 178.4 (2) |
C5B—C4—C9—C8 | −7 (3) | C30—C31—C32—C27 | −0.3 (4) |
C7—C8—C9—C4 | 14.8 (3) | C39—P2—C33—C34 | 7.8 (2) |
C7—C8—C9—C10 | −165.2 (2) | C20—P2—C33—C34 | 119.89 (19) |
C2—C1—C10—C9 | 3.7 (3) | Rh1—P2—C33—C34 | −110.98 (18) |
P1—C1—C10—C9 | −165.56 (16) | C39—P2—C33—C38 | −178.27 (18) |
C2—C1—C10—C11 | −175.3 (2) | C20—P2—C33—C38 | −66.1 (2) |
P1—C1—C10—C11 | 15.4 (3) | Rh1—P2—C33—C38 | 63.00 (19) |
C4—C9—C10—C1 | 0.6 (3) | C38—C33—C34—C35 | 1.0 (3) |
C8—C9—C10—C1 | −179.4 (2) | P2—C33—C34—C35 | 174.93 (19) |
C4—C9—C10—C11 | 179.74 (19) | C33—C34—C35—C36 | −0.1 (4) |
C8—C9—C10—C11 | −0.3 (3) | C34—C35—C36—C37 | −0.5 (4) |
C1—C10—C11—C20 | −83.5 (3) | C35—C36—C37—C38 | 0.2 (4) |
C9—C10—C11—C20 | 97.4 (2) | C36—C37—C38—C33 | 0.7 (4) |
C1—C10—C11—C12 | 103.2 (2) | C34—C33—C38—C37 | −1.3 (4) |
C9—C10—C11—C12 | −75.9 (2) | P2—C33—C38—C37 | −175.47 (19) |
C20—C11—C12—C17 | −3.1 (3) | C33—P2—C39—C44 | 57.7 (2) |
C10—C11—C12—C17 | 170.3 (2) | C20—P2—C39—C44 | −52.3 (2) |
C20—C11—C12—C13 | 178.8 (2) | Rh1—P2—C39—C44 | 177.79 (17) |
C10—C11—C12—C13 | −7.8 (3) | C33—P2—C39—C40 | −122.44 (18) |
C17—C12—C13—C14 | 16.9 (3) | C20—P2—C39—C40 | 127.50 (18) |
C11—C12—C13—C14 | −165.0 (2) | Rh1—P2—C39—C40 | −2.4 (2) |
C12—C13—C14—C15 | −45.3 (3) | C44—C39—C40—C41 | −0.5 (3) |
C13—C14—C15—C16 | 62.5 (3) | P2—C39—C40—C41 | 179.70 (18) |
C14—C15—C16—C17 | −50.2 (3) | C39—C40—C41—C42 | −1.0 (4) |
C11—C12—C17—C18 | −4.2 (3) | C40—C41—C42—C43 | 1.4 (4) |
C13—C12—C17—C18 | 173.9 (2) | C41—C42—C43—C44 | −0.3 (4) |
C11—C12—C17—C16 | 176.4 (2) | C42—C43—C44—C39 | −1.3 (4) |
C13—C12—C17—C16 | −5.6 (3) | C40—C39—C44—C43 | 1.6 (3) |
C15—C16—C17—C18 | −156.8 (2) | P2—C39—C44—C43 | −178.55 (19) |
C15—C16—C17—C12 | 22.6 (3) | C52—C45—C46—C47 | −5.0 (4) |
C12—C17—C18—C19 | 6.8 (4) | Rh1—C45—C46—C47 | −105.3 (2) |
C16—C17—C18—C19 | −173.7 (2) | C52—C45—C46—Rh1 | 100.3 (3) |
C17—C18—C19—C20 | −2.0 (4) | C45—C46—C47—C48 | 94.6 (3) |
C18—C19—C20—C11 | −5.3 (3) | Rh1—C46—C47—C48 | 10.6 (3) |
C18—C19—C20—P2 | 169.38 (19) | C46—C47—C48—C49 | −36.2 (3) |
C12—C11—C20—C19 | 7.8 (3) | C47—C48—C49—C50 | −39.1 (4) |
C10—C11—C20—C19 | −165.4 (2) | C47—C48—C49—Rh1 | 42.6 (3) |
C12—C11—C20—P2 | −166.86 (16) | C48—C49—C50—C51 | −4.7 (4) |
C10—C11—C20—P2 | 19.9 (3) | Rh1—C49—C50—C51 | −104.3 (3) |
C39—P2—C20—C19 | 123.92 (19) | C48—C49—C50—Rh1 | 99.6 (2) |
C33—P2—C20—C19 | 13.1 (2) | C49—C50—C51—C52 | 96.5 (3) |
Rh1—P2—C20—C19 | −111.57 (17) | Rh1—C50—C51—C52 | 14.4 (3) |
C39—P2—C20—C11 | −61.52 (19) | C46—C45—C52—C51 | −37.7 (4) |
C33—P2—C20—C11 | −172.33 (17) | Rh1—C45—C52—C51 | 43.2 (3) |
Rh1—P2—C20—C11 | 62.99 (18) | C50—C51—C52—C45 | −38.7 (4) |
Complex | Rh—P | Rh—CM | P—Rh—P | CM—Rh—CM |
[[Rh(H8-BINAP)(cod)](BF4) | 2.3187 (6), 2.3343 (6) | 2.116 (4), 2.140 (4) | 91.055 (9) | 83.80 (3) |
[Rh(H8-BINAP)(cod)](ClO4) | 2.326, 2.337 | 2.143, 2.245 | 90.58 | 84.66 |
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