metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoIUCrDATA
ISSN: 2414-3146

(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

Edited by S. Parkin, University of Kentucky, USA (Received 18 July 2017; accepted 28 August 2017; online 5 September 2017)

The title compound, [Rh(C8H12)(C44H20P2)]BF4·0.72C5H12·0.56·CH4O, crystallizes in the Sohncke space group 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 asymmetric unit 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[Shibata, T., Kurakawa, H. & Kanda, K. (2007). J. Org. Chem. 72, 6521-6525.]). J. Org. Chem. 72, 6521–6525].

3D view (loading...)
[Scheme 3D1]
Chemical scheme
[Scheme 1]

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[Miyashita, A., Yasuda, A., Takaya, H., Toriumi, K., Ito, T., Souchi, T. & Noyori, R. (1980). J. Am. Chem. Soc. 102, 7932-7934.]).

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[Zhang, X., Mashima, K., Koyano, K., Sayo, N., Kumobayashi, H., Akutagawa, S. & Takaya, H. (1994). J. Chem. Soc. Perkin Trans. 1, pp. 2309-2322.]). 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 space group P21 as red prisms. This is isomorphous to the related perchlorate complex [Rh(H8-BINAP)(cod)]ClO4 (Zhang et al., 1994[Zhang, X., Mashima, K., Koyano, K., Sayo, N., Kumobayashi, H., Akutagawa, S. & Takaya, H. (1994). J. Chem. Soc. Perkin Trans. 1, pp. 2309-2322.]). 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[link]). The asymmetric unit contains one cation, one anion, and cocrystallized pentane (0.72) and methanol (2 × 0.28) mol­ecules.

[Figure 1]
Figure 1
A view of the [Rh(H8-BINAP)(cod)]+ cation, with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms have been omitted for clarity.

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[link]), 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[Preetz, A., Fischer, C., Kohrt, C., Drexler, H.-J., Baumann, W. & Heller, D. (2011). Organometallics, 30, 5155-5159.], and references therein). Comparable distances, e.g. Rh—P (Table 1[link]), 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[Preetz, A., Drexler, H.-J., Schulz, S. & Heller, D. (2010). Tetrahedron Asymmetry, 21, 1226-1231.]).

Table 1
Selected distances (Å) and angles (°) of the rhodium/H8-BINAP cod complexes (CM = centroids of the double bonds of the olefin)

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

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[Shibata, T., Kurakawa, H. & Kanda, K. (2007). J. Org. Chem. 72, 6521-6525.]). 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[Drexler, H.-J., Preetz, A., Schmidt, T. & Heller, D. (2007). Handbook of Homogeneous Hydrogenation, edited by J. G. de Vries & C. J. Elsevier, pp. 257-293. Weinheim: Wiley-VCH.]).

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[link] 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 k2nnbd/k2cod 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[Meissner, A., Alberico, E., Drexler, H.-J., Baumann, W. & Heller, D. (2014). Catal. Sci. Technol. 4, 3409-3425.]).

[Figure 2]
Figure 2
First part (first double bond) of the hydrogen consumption for the hydrogenation 0.0050 mmol [Rh(H8-BINAP)(nbd)](BF4), 4.77 mmol nb d, 15.0 ml MeOH, 298 K, normal pressure (blue) and 0.0044 mmol [Rh(H8-BINAP)(cod)](BF4), 1.84 mmol cod, 15.0 ml MeOH, 298 K, normal pressure (red).

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[Drexler, H.-J., Preetz, A., Schmidt, T. & Heller, D. (2007). Handbook of Homogeneous Hydrogenation, edited by J. G. de Vries & C. J. Elsevier, pp. 257-293. Weinheim: Wiley-VCH.]).

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[Schrock, R. R. & Osborn, J. A. (1971). J. Am. Chem. Soc. 93, 2397-2407.]). 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 refinement details are summarized in Table 2[link]. The absolute configuration R for the title compound was determined using 5105 quotients in the refinement. The Flack parameter at convergence was −0.008 (3).

Table 2
Experimental details

Crystal data
Chemical formula [Rh(C8H12)(C44H20P2)]BF4·0.72C5H12·0.56CH4O
Mr 998.48
Crystal system, space group Monoclinic, P21
Temperature (K) 150
a, b, c (Å) 11.0916 (2), 15.3047 (3), 14.1459 (3)
β (°) 94.260 (1)
V3) 2394.68 (8)
Z 2
Radiation type Mo Kα
μ (mm−1) 0.48
Crystal size (mm) 0.50 × 0.42 × 0.22
 
Data collection
Diffractometer Bruker APEXII CCD
Absorption correction Multi-scan (SADABS; Bruker, 2014[Bruker (2014). APEX2 and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.])
Tmin, Tmax 0.686, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections 125039, 10991, 10761
Rint 0.029
(sin θ/λ)max−1) 0.649
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.019, 0.049, 1.04
No. of reflections 10991
No. of parameters 685
No. of restraints 260
H-atom treatment H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3) 0.30, −0.30
Absolute structure Flack x determined using 5105 quotients [(I+) − (I)]/[(I+) + (I)] (Parsons et al., 2013[Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249-259.])
Absolute structure parameter −0.008 (3)
Computer programs: APEX2 (Bruker, 2014[Bruker (2014). APEX2 and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SAINT (Bruker, 2013[Bruker (2013). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]), SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

After refinement of the BF4 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; refinement 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.

Atoms 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


Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: 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).

(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 top
Crystal data top
[Rh(C8H12)(C44H20P2)]BF4·0.72C5H12·0.56CH4OF(000) = 1041
Mr = 998.48Dx = 1.385 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
a = 11.0916 (2) ÅCell parameters from 9769 reflections
b = 15.3047 (3) Åθ = 2.3–27.5°
c = 14.1459 (3) ŵ = 0.48 mm1
β = 94.260 (1)°T = 150 K
V = 2394.68 (8) Å3Prism, red
Z = 20.50 × 0.42 × 0.22 mm
Data collection top
Bruker APEXII CCD
diffractometer
10991 independent reflections
Radiation source: fine-focus sealed tube10761 reflections with I > 2σ(I)
Detector resolution: 8.3333 pixels mm-1Rint = 0.029
φ and ω scansθmax = 27.5°, θmin = 1.4°
Absorption correction: multi-scan
(SADABS; Bruker, 2014)
h = 1414
Tmin = 0.686, Tmax = 0.746k = 1919
125039 measured reflectionsl = 1818
Refinement top
Refinement on F2Hydrogen site location: mixed
Least-squares matrix: fullH 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 = 1.04Δρmax = 0.30 e Å3
10991 reflectionsΔρmin = 0.30 e Å3
685 parametersAbsolute structure: Flack x determined using 5105 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
260 restraintsAbsolute structure parameter: 0.008 (3)
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Rh10.82304 (2)0.75126 (2)0.80792 (2)0.01878 (4)
P10.74750 (5)0.82768 (4)0.67490 (4)0.01918 (10)
P20.84440 (5)0.88047 (3)0.89523 (4)0.01791 (10)
C10.64594 (19)0.91929 (14)0.69716 (15)0.0201 (4)
C20.5207 (2)0.90898 (16)0.68133 (17)0.0264 (5)
H20.48920.86070.64520.032*
C30.4425 (2)0.96830 (17)0.71766 (18)0.0291 (5)
H30.35790.95940.70690.035*
C40.4843 (2)1.04049 (16)0.76942 (16)0.0244 (4)
C50.3906 (8)1.0986 (9)0.8093 (15)0.0285 (16)0.720 (4)
H5A0.36541.07300.86900.034*0.720 (4)
H5B0.31851.10190.76380.034*0.720 (4)
C60.4394 (3)1.1894 (3)0.8284 (3)0.0334 (8)0.720 (4)
H6A0.38151.22360.86350.040*0.720 (4)
H6B0.45011.21960.76770.040*0.720 (4)
C70.5611 (3)1.1837 (2)0.8869 (3)0.0326 (7)0.720 (4)
H7A0.58931.24330.90440.039*0.720 (4)
H7B0.55061.15100.94610.039*0.720 (4)
C80.6557 (2)1.13826 (16)0.83163 (17)0.0271 (5)0.720 (4)
H8A0.68451.17950.78430.033*0.720 (4)
H8B0.72581.12260.87590.033*0.720 (4)
C5B0.402 (2)1.102 (2)0.820 (4)0.0285 (16)0.280 (4)
H5C0.34071.12460.77130.034*0.280 (4)
H5D0.35811.06650.86440.034*0.280 (4)
C6B0.4524 (9)1.1816 (7)0.8755 (8)0.0334 (8)0.280 (4)
H6C0.39021.22790.87560.040*0.280 (4)
H6D0.47541.16470.94190.040*0.280 (4)
C7B0.5621 (8)1.2150 (6)0.8290 (7)0.0326 (7)0.280 (4)
H7C0.59701.26620.86390.039*0.280 (4)
H7D0.53941.23260.76270.039*0.280 (4)
C8B0.6557 (2)1.13826 (16)0.83163 (17)0.0271 (5)0.280 (4)
H8C0.72911.15830.80220.033*0.280 (4)
H8D0.67961.12360.89860.033*0.280 (4)
C90.60854 (19)1.05614 (14)0.78088 (15)0.0207 (4)
C100.68938 (19)0.99491 (14)0.74490 (15)0.0196 (4)
C110.82155 (18)1.01648 (14)0.75959 (15)0.0191 (4)
C120.86869 (19)1.08103 (14)0.70159 (15)0.0217 (4)
C130.7911 (2)1.11869 (16)0.61848 (16)0.0263 (4)
H13A0.73001.15810.64320.032*
H13B0.74721.07030.58460.032*
C140.8620 (2)1.16937 (18)0.54775 (18)0.0331 (5)
H14A0.90501.12780.50850.040*
H14B0.80531.20370.50510.040*
C150.9530 (2)1.23048 (15)0.5990 (2)0.0332 (6)
H15A0.91061.27150.63930.040*
H15B0.99501.26500.55230.040*
C161.0447 (2)1.17733 (17)0.6602 (2)0.0321 (5)
H16A1.09791.14570.61860.039*
H16B1.09591.21760.70060.039*
C170.9862 (2)1.11201 (15)0.72283 (17)0.0253 (4)
C181.0511 (2)1.08231 (17)0.80484 (19)0.0296 (5)
H181.12741.10780.82330.036*
C191.0069 (2)1.01666 (16)0.85966 (17)0.0262 (4)
H191.05400.99630.91410.031*
C200.89329 (18)0.97999 (14)0.83567 (15)0.0197 (4)
C210.66148 (18)0.75831 (19)0.58804 (14)0.0239 (4)
C220.7066 (2)0.73540 (17)0.50185 (16)0.0307 (6)
H220.78010.76040.48420.037*
C230.6440 (3)0.6759 (2)0.44154 (19)0.0396 (6)
H230.67610.65980.38360.047*
C240.5358 (3)0.6400 (2)0.4653 (2)0.0429 (7)
H240.49270.60070.42330.051*
C250.4909 (2)0.66176 (19)0.5506 (2)0.0352 (6)
H250.41630.63770.56700.042*
C260.5540 (2)0.71860 (17)0.61255 (18)0.0287 (5)
H260.52410.73080.67240.034*
C270.8710 (2)0.87183 (15)0.61120 (17)0.0270 (5)
C280.9896 (2)0.85627 (18)0.64660 (19)0.0346 (6)
H281.00530.82130.70160.041*
C291.0854 (3)0.8923 (2)0.6008 (3)0.0503 (9)
H291.16630.88280.62570.060*
C301.0637 (4)0.9411 (2)0.5207 (3)0.0601 (11)
H301.12930.96580.49040.072*
C310.9461 (4)0.95470 (19)0.4834 (2)0.0523 (9)
H310.93160.98760.42680.063*
C320.8490 (3)0.92039 (17)0.52838 (19)0.0369 (6)
H320.76840.93000.50280.044*
C330.9548 (2)0.86850 (14)0.99747 (16)0.0221 (4)
C340.9212 (2)0.86878 (15)1.09020 (17)0.0263 (4)
H340.83950.88001.10240.032*
C351.0070 (3)0.85256 (17)1.16552 (18)0.0345 (6)
H350.98350.85291.22870.041*
C361.1260 (3)0.83602 (18)1.1485 (2)0.0384 (6)
H361.18420.82551.19990.046*
C371.1599 (2)0.83480 (18)1.0566 (2)0.0356 (6)
H371.24160.82321.04500.043*
C381.0753 (2)0.85041 (16)0.98093 (18)0.0285 (5)
H381.09930.84880.91790.034*
C390.7030 (2)0.90642 (15)0.94537 (16)0.0206 (4)
C400.6040 (2)0.85126 (15)0.92366 (15)0.0226 (4)
H400.61220.80220.88350.027*
C410.4933 (2)0.86829 (17)0.96094 (18)0.0289 (5)
H410.42570.83150.94540.035*
C420.4827 (2)0.93896 (18)1.02050 (19)0.0333 (5)
H420.40790.94971.04700.040*
C430.5796 (2)0.99438 (17)1.04220 (18)0.0317 (5)
H430.57101.04291.08300.038*
C440.6896 (2)0.97870 (16)1.00391 (16)0.0256 (4)
H440.75571.01731.01760.031*
C450.8571 (3)0.63513 (16)0.71861 (17)0.0312 (5)
H450.854 (3)0.658 (2)0.6563 (13)0.037*
C460.7485 (2)0.62307 (16)0.75734 (17)0.0289 (5)
H460.6797 (19)0.638 (2)0.7163 (19)0.035*
C470.7242 (3)0.56199 (17)0.83809 (19)0.0341 (5)
H47A0.78280.51310.83940.041*
H47B0.64210.53710.82660.041*
C480.7341 (3)0.60797 (18)0.9345 (2)0.0343 (6)
H48A0.65570.63590.94480.041*
H48B0.75030.56370.98490.041*
C490.8322 (2)0.67644 (16)0.94369 (16)0.0286 (5)
H490.825 (3)0.7198 (16)0.9912 (17)0.034*
C500.9438 (2)0.66987 (16)0.90917 (18)0.0298 (5)
H501.002 (2)0.7099 (17)0.933 (2)0.036*
C510.9928 (3)0.59022 (19)0.8617 (2)0.0389 (6)
H51A0.95100.53750.88340.047*
H51B1.07990.58420.88120.047*
C520.9760 (3)0.5953 (2)0.7534 (2)0.0419 (7)
H52A1.04240.63040.72980.050*
H52B0.98140.53570.72690.050*
B10.3031 (12)0.7140 (7)0.7996 (7)0.057 (3)0.465 (8)
F10.4258 (13)0.7105 (12)0.8181 (14)0.067 (4)0.465 (8)
F20.2657 (7)0.6820 (9)0.7125 (6)0.110 (3)0.465 (8)
F30.2551 (10)0.6727 (7)0.8737 (9)0.097 (3)0.465 (8)
F40.2698 (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)
O710.4066 (17)0.9398 (14)0.4145 (13)0.126 (7)0.280 (4)
H710.39020.92650.46970.189*0.280 (4)
C710.3348 (19)0.889 (2)0.348 (2)0.114 (10)0.280 (4)
H71A0.37700.88240.29040.171*0.280 (4)
H71B0.25740.91890.33340.171*0.280 (4)
H71C0.32030.83170.37560.171*0.280 (4)
O610.7249 (11)0.9616 (14)0.2888 (11)0.100 (4)0.280 (4)
H610.74701.01190.27350.150*0.280 (4)
C610.5993 (7)0.9633 (4)0.3056 (4)0.1080 (19)0.280 (4)
H61A0.57011.02380.30280.162*0.280 (4)
H61B0.58830.93890.36840.162*0.280 (4)
H61C0.55340.92850.25720.162*0.280 (4)
C730.6896 (10)0.9051 (6)0.2781 (6)0.098 (3)0.720 (4)
H73A0.73560.93300.22980.148*0.720 (4)
H73B0.65150.85170.25200.148*0.720 (4)
H73C0.74430.89040.33340.148*0.720 (4)
C740.5993 (7)0.9633 (4)0.3056 (4)0.1080 (19)0.720 (4)
H74A0.63771.01580.33550.130*0.720 (4)
H74B0.54810.98220.24900.130*0.720 (4)
C750.5288 (9)0.9228 (8)0.3685 (10)0.154 (4)0.720 (4)
H75A0.53370.95790.42750.184*0.720 (4)
H75B0.56590.86530.38450.184*0.720 (4)
C760.3983 (12)0.9077 (13)0.3401 (13)0.170 (5)0.720 (4)
H76A0.35550.96330.32460.204*0.720 (4)
H76B0.38740.86760.28520.204*0.720 (4)
C770.3581 (8)0.8689 (7)0.4240 (8)0.110 (3)0.720 (4)
H77A0.27480.84830.41160.164*0.720 (4)
H77B0.36130.91240.47500.164*0.720 (4)
H77C0.41060.81950.44310.164*0.720 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Rh10.01974 (7)0.01788 (7)0.01896 (7)0.00079 (7)0.00298 (5)0.00042 (7)
P10.0202 (2)0.0204 (2)0.0174 (2)0.00308 (19)0.00387 (19)0.00066 (19)
P20.0161 (2)0.0194 (2)0.0184 (2)0.00075 (19)0.00228 (18)0.00018 (19)
C10.0196 (9)0.0221 (10)0.0186 (9)0.0001 (8)0.0020 (7)0.0026 (8)
C20.0226 (10)0.0240 (11)0.0319 (12)0.0017 (8)0.0031 (9)0.0006 (9)
C30.0144 (9)0.0334 (12)0.0386 (13)0.0011 (9)0.0033 (9)0.0045 (10)
C40.0204 (10)0.0286 (11)0.0242 (10)0.0033 (8)0.0028 (8)0.0080 (8)
C50.018 (2)0.0358 (18)0.031 (5)0.0054 (16)0.003 (3)0.0032 (14)
C60.0302 (16)0.0332 (16)0.037 (2)0.0115 (12)0.0025 (18)0.0035 (18)
C70.0295 (15)0.0326 (17)0.0357 (18)0.0058 (13)0.0024 (14)0.0112 (13)
C80.0239 (10)0.0273 (11)0.0302 (11)0.0020 (9)0.0023 (9)0.0049 (9)
C5B0.018 (2)0.0358 (18)0.031 (5)0.0054 (16)0.003 (3)0.0032 (14)
C6B0.0302 (16)0.0332 (16)0.037 (2)0.0115 (12)0.0025 (18)0.0035 (18)
C7B0.0295 (15)0.0326 (17)0.0357 (18)0.0058 (13)0.0024 (14)0.0112 (13)
C8B0.0239 (10)0.0273 (11)0.0302 (11)0.0020 (9)0.0023 (9)0.0049 (9)
C90.0200 (10)0.0227 (10)0.0196 (9)0.0008 (8)0.0020 (7)0.0046 (8)
C100.0180 (9)0.0225 (10)0.0182 (9)0.0014 (8)0.0012 (7)0.0036 (7)
C110.0164 (9)0.0193 (9)0.0221 (10)0.0019 (7)0.0042 (7)0.0025 (8)
C120.0209 (10)0.0212 (10)0.0234 (10)0.0003 (8)0.0044 (8)0.0008 (8)
C130.0261 (11)0.0258 (11)0.0269 (11)0.0031 (9)0.0014 (8)0.0052 (9)
C140.0393 (13)0.0318 (13)0.0287 (12)0.0035 (11)0.0055 (10)0.0048 (10)
C150.0349 (12)0.0269 (14)0.0384 (13)0.0056 (9)0.0066 (10)0.0087 (9)
C160.0258 (11)0.0279 (12)0.0438 (14)0.0053 (9)0.0096 (10)0.0087 (10)
C170.0199 (10)0.0222 (10)0.0346 (12)0.0016 (8)0.0078 (8)0.0039 (9)
C180.0179 (10)0.0297 (12)0.0409 (13)0.0056 (9)0.0001 (9)0.0032 (10)
C190.0199 (10)0.0272 (11)0.0310 (11)0.0015 (8)0.0018 (8)0.0021 (9)
C200.0174 (9)0.0196 (10)0.0226 (10)0.0015 (7)0.0042 (7)0.0006 (8)
C210.0259 (9)0.0249 (11)0.0205 (8)0.0011 (11)0.0009 (7)0.0010 (10)
C220.0311 (11)0.0378 (17)0.0233 (10)0.0029 (10)0.0019 (8)0.0058 (9)
C230.0396 (14)0.0521 (17)0.0265 (12)0.0009 (13)0.0008 (10)0.0148 (12)
C240.0384 (14)0.0485 (17)0.0400 (15)0.0066 (13)0.0091 (11)0.0178 (13)
C250.0267 (12)0.0375 (14)0.0406 (14)0.0063 (10)0.0038 (10)0.0061 (11)
C260.0285 (12)0.0293 (11)0.0285 (11)0.0054 (9)0.0043 (9)0.0056 (9)
C270.0310 (11)0.0259 (11)0.0259 (11)0.0082 (9)0.0134 (9)0.0062 (9)
C280.0295 (12)0.0378 (14)0.0381 (13)0.0101 (10)0.0141 (10)0.0135 (11)
C290.0358 (15)0.0528 (18)0.066 (2)0.0217 (14)0.0280 (14)0.0252 (16)
C300.069 (2)0.0457 (18)0.073 (2)0.0285 (17)0.053 (2)0.0211 (17)
C310.090 (3)0.0296 (14)0.0422 (16)0.0148 (15)0.0405 (17)0.0056 (12)
C320.0573 (17)0.0269 (12)0.0291 (12)0.0066 (11)0.0202 (12)0.0013 (10)
C330.0231 (10)0.0182 (10)0.0242 (10)0.0018 (8)0.0037 (8)0.0000 (8)
C340.0301 (11)0.0222 (11)0.0261 (11)0.0003 (9)0.0012 (9)0.0020 (8)
C350.0480 (15)0.0289 (12)0.0250 (12)0.0011 (11)0.0076 (10)0.0044 (10)
C360.0403 (14)0.0304 (13)0.0412 (15)0.0016 (11)0.0182 (11)0.0087 (11)
C370.0244 (11)0.0301 (13)0.0506 (16)0.0005 (10)0.0079 (10)0.0063 (11)
C380.0241 (11)0.0257 (11)0.0352 (12)0.0011 (9)0.0005 (9)0.0023 (9)
C390.0198 (10)0.0245 (11)0.0178 (10)0.0016 (8)0.0038 (8)0.0042 (8)
C400.0220 (10)0.0238 (10)0.0226 (10)0.0004 (8)0.0059 (8)0.0026 (8)
C410.0230 (11)0.0325 (12)0.0322 (12)0.0003 (9)0.0083 (9)0.0044 (10)
C420.0282 (12)0.0390 (13)0.0345 (13)0.0092 (10)0.0146 (10)0.0035 (11)
C430.0372 (13)0.0319 (12)0.0269 (12)0.0097 (10)0.0092 (10)0.0014 (9)
C440.0277 (11)0.0266 (11)0.0228 (10)0.0027 (9)0.0030 (8)0.0003 (9)
C450.0477 (15)0.0218 (11)0.0244 (11)0.0043 (10)0.0057 (10)0.0028 (9)
C460.0373 (13)0.0212 (11)0.0273 (11)0.0043 (9)0.0034 (9)0.0027 (9)
C470.0416 (14)0.0250 (12)0.0354 (13)0.0091 (10)0.0002 (11)0.0028 (10)
C480.0447 (16)0.0283 (13)0.0301 (13)0.0053 (11)0.0044 (11)0.0066 (10)
C490.0414 (13)0.0225 (11)0.0216 (11)0.0009 (10)0.0006 (9)0.0014 (9)
C500.0325 (12)0.0217 (11)0.0338 (12)0.0002 (9)0.0075 (10)0.0005 (9)
C510.0366 (14)0.0298 (13)0.0496 (16)0.0107 (11)0.0016 (12)0.0003 (11)
C520.0438 (15)0.0362 (14)0.0473 (16)0.0141 (12)0.0145 (13)0.0012 (12)
B10.038 (5)0.061 (5)0.075 (6)0.012 (4)0.011 (5)0.015 (5)
F10.045 (5)0.083 (9)0.076 (5)0.007 (4)0.020 (4)0.033 (5)
F20.087 (4)0.156 (9)0.084 (5)0.009 (5)0.016 (4)0.050 (5)
F30.068 (4)0.111 (7)0.117 (6)0.009 (5)0.032 (4)0.050 (6)
F40.081 (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)
O710.138 (16)0.152 (18)0.090 (11)0.023 (13)0.016 (10)0.034 (11)
C710.056 (11)0.16 (3)0.115 (18)0.014 (14)0.047 (12)0.002 (19)
O610.104 (9)0.124 (11)0.070 (7)0.011 (9)0.006 (7)0.008 (9)
C610.155 (5)0.088 (4)0.087 (4)0.022 (4)0.046 (4)0.019 (3)
C730.160 (8)0.077 (5)0.058 (4)0.017 (5)0.008 (5)0.000 (4)
C740.155 (5)0.088 (4)0.087 (4)0.022 (4)0.046 (4)0.019 (3)
C750.129 (7)0.125 (7)0.207 (9)0.004 (6)0.013 (7)0.035 (7)
C760.152 (10)0.155 (10)0.194 (11)0.025 (9)0.048 (10)0.055 (9)
C770.080 (5)0.096 (6)0.150 (9)0.003 (5)0.011 (6)0.019 (6)
Geometric parameters (Å, º) top
Rh1—C462.226 (2)C29—C301.364 (6)
Rh1—C452.229 (2)C29—H290.9500
Rh1—C492.232 (2)C30—C311.386 (6)
Rh1—C502.261 (2)C30—H300.9500
Rh1—P12.3187 (6)C31—C321.394 (4)
Rh1—P22.3343 (6)C31—H310.9500
P1—C271.824 (2)C32—H320.9500
P1—C211.837 (2)C33—C341.390 (3)
P1—C11.840 (2)C33—C381.402 (3)
P2—C391.812 (2)C34—C351.398 (3)
P2—C331.833 (2)C34—H340.9500
P2—C201.842 (2)C35—C361.382 (4)
C1—C21.399 (3)C35—H350.9500
C1—C101.407 (3)C36—C371.379 (4)
C2—C31.381 (3)C36—H360.9500
C2—H20.9500C37—C381.391 (4)
C3—C41.386 (4)C37—H370.9500
C3—H30.9500C38—H380.9500
C4—C91.397 (3)C39—C441.396 (3)
C4—C51.509 (8)C39—C401.401 (3)
C4—C5B1.53 (2)C40—C411.396 (3)
C5—C61.509 (11)C40—H400.9500
C5—H5A0.9900C41—C421.381 (4)
C5—H5B0.9900C41—H410.9500
C6—C71.532 (5)C42—C431.386 (4)
C6—H6A0.9900C42—H420.9500
C6—H6B0.9900C43—C441.392 (3)
C7—C81.523 (4)C43—H430.9500
C7—H7A0.9900C44—H440.9500
C7—H7B0.9900C45—C461.372 (4)
C8—C91.521 (3)C45—C521.503 (4)
C8—H8A0.9900C45—H450.946 (14)
C8—H8B0.9900C46—C471.516 (3)
C5B—C6B1.53 (2)C46—H460.953 (13)
C5B—H5C0.9900C47—C481.532 (4)
C5B—H5D0.9900C47—H47A0.9900
C6B—C7B1.514 (13)C47—H47B0.9900
C6B—H6C0.9900C48—C491.509 (4)
C6B—H6D0.9900C48—H48A0.9900
C7B—H7C0.9900C48—H48B0.9900
C7B—H7D0.9900C49—C501.368 (4)
C9—C101.417 (3)C49—H490.952 (14)
C10—C111.502 (3)C50—C511.512 (4)
C11—C201.406 (3)C50—H500.939 (14)
C11—C121.409 (3)C51—C521.531 (4)
C12—C171.398 (3)C51—H51A0.9900
C12—C131.518 (3)C51—H51B0.9900
C13—C141.529 (3)C52—H52A0.9900
C13—H13A0.9900C52—H52B0.9900
C13—H13B0.9900B1—F21.362 (9)
C14—C151.520 (4)B1—F31.366 (9)
C14—H14A0.9900B1—F11.368 (9)
C14—H14B0.9900B1—F41.375 (9)
C15—C161.522 (4)B1'—F4'1.357 (8)
C15—H15A0.9900B1'—F3'1.362 (8)
C15—H15B0.9900B1'—F1'1.374 (8)
C16—C171.514 (3)B1'—F2'1.377 (9)
C16—H16A0.9900O71—C711.411 (13)
C16—H16B0.9900O71—H710.8400
C17—C181.395 (4)C71—H71A0.9800
C18—C191.381 (3)C71—H71B0.9800
C18—H180.9500C71—H71C0.9800
C19—C201.398 (3)O61—C611.431 (11)
C19—H190.9500O61—H610.8400
C21—C221.397 (3)C61—H61A0.9800
C21—C261.405 (3)C61—H61B0.9800
C22—C231.397 (4)C61—H61C0.9800
C22—H220.9500C73—H73A0.9800
C23—C241.384 (4)C73—H73B0.9800
C23—H230.9500C73—H73C0.9800
C24—C251.380 (4)C75—C761.491 (15)
C24—H240.9500C75—H75A0.9900
C25—C261.387 (4)C75—H75B0.9900
C25—H250.9500C76—C771.428 (15)
C26—H260.9500C76—H76A0.9900
C27—C281.392 (4)C76—H76B0.9900
C27—C321.394 (4)C77—H77A0.9800
C28—C291.399 (4)C77—H77B0.9800
C28—H280.9500C77—H77C0.9800
C46—Rh1—C4535.86 (10)C28—C27—C32119.7 (2)
C46—Rh1—C4979.42 (9)C28—C27—P1118.86 (19)
C45—Rh1—C4994.58 (9)C32—C27—P1121.4 (2)
C46—Rh1—C5084.63 (9)C27—C28—C29119.7 (3)
C45—Rh1—C5078.61 (9)C27—C28—H28120.1
C49—Rh1—C5035.44 (10)C29—C28—H28120.1
C46—Rh1—P194.63 (7)C30—C29—C28120.5 (3)
C45—Rh1—P190.48 (7)C30—C29—H29119.8
C49—Rh1—P1161.39 (7)C28—C29—H29119.8
C50—Rh1—P1162.43 (7)C29—C30—C31120.1 (3)
C46—Rh1—P2159.61 (7)C29—C30—H30119.9
C45—Rh1—P2163.86 (7)C31—C30—H30119.9
C49—Rh1—P289.02 (6)C30—C31—C32120.5 (3)
C50—Rh1—P295.71 (7)C30—C31—H31119.8
P1—Rh1—P291.055 (19)C32—C31—H31119.8
C27—P1—C21104.80 (10)C27—C32—C31119.4 (3)
C27—P1—C1107.09 (10)C27—C32—H32120.3
C21—P1—C1105.11 (11)C31—C32—H32120.3
C27—P1—Rh1110.39 (9)C34—C33—C38118.9 (2)
C21—P1—Rh1112.94 (9)C34—C33—P2122.28 (18)
C1—P1—Rh1115.74 (7)C38—C33—P2118.50 (17)
C39—P2—C33105.05 (10)C33—C34—C35120.2 (2)
C39—P2—C20106.89 (10)C33—C34—H34119.9
C33—P2—C20103.98 (10)C35—C34—H34119.9
C39—P2—Rh1109.63 (8)C36—C35—C34120.3 (2)
C33—P2—Rh1111.61 (7)C36—C35—H35119.8
C20—P2—Rh1118.71 (7)C34—C35—H35119.8
C2—C1—C10118.0 (2)C37—C36—C35119.8 (2)
C2—C1—P1119.98 (17)C37—C36—H36120.1
C10—C1—P1121.11 (16)C35—C36—H36120.1
C3—C2—C1120.6 (2)C36—C37—C38120.5 (2)
C3—C2—H2119.7C36—C37—H37119.7
C1—C2—H2119.7C38—C37—H37119.7
C2—C3—C4121.8 (2)C37—C38—C33120.2 (2)
C2—C3—H3119.1C37—C38—H38119.9
C4—C3—H3119.1C33—C38—H38119.9
C3—C4—C9119.1 (2)C44—C39—C40119.4 (2)
C3—C4—C5117.1 (4)C44—C39—P2122.61 (18)
C9—C4—C5123.8 (4)C40—C39—P2117.98 (18)
C3—C4—C5B123.6 (9)C41—C40—C39120.1 (2)
C9—C4—C5B117.3 (10)C41—C40—H40119.9
C4—C5—C6111.3 (7)C39—C40—H40119.9
C4—C5—H5A109.4C42—C41—C40119.6 (2)
C6—C5—H5A109.4C42—C41—H41120.2
C4—C5—H5B109.4C40—C41—H41120.2
C6—C5—H5B109.4C41—C42—C43121.0 (2)
H5A—C5—H5B108.0C41—C42—H42119.5
C5—C6—C7109.5 (7)C43—C42—H42119.5
C5—C6—H6A109.8C42—C43—C44119.7 (2)
C7—C6—H6A109.8C42—C43—H43120.1
C5—C6—H6B109.8C44—C43—H43120.1
C7—C6—H6B109.8C43—C44—C39120.2 (2)
H6A—C6—H6B108.2C43—C44—H44119.9
C8—C7—C6111.2 (3)C39—C44—H44119.9
C8—C7—H7A109.4C46—C45—C52126.1 (2)
C6—C7—H7A109.4C46—C45—Rh171.96 (14)
C8—C7—H7B109.4C52—C45—Rh1108.63 (18)
C6—C7—H7B109.4C46—C45—H45117 (2)
H7A—C7—H7B108.0C52—C45—H45115 (2)
C9—C8—C7113.2 (2)Rh1—C45—H45104 (2)
C9—C8—H8A108.9C45—C46—C47126.5 (2)
C7—C8—H8A108.9C45—C46—Rh172.18 (14)
C9—C8—H8B108.9C47—C46—Rh1112.58 (16)
C7—C8—H8B108.9C45—C46—H46114.2 (19)
H8A—C8—H8B107.8C47—C46—H46116 (2)
C6B—C5B—C4121.5 (17)Rh1—C46—H46104 (2)
C6B—C5B—H5C106.9C46—C47—C48112.5 (2)
C4—C5B—H5C106.9C46—C47—H47A109.1
C6B—C5B—H5D106.9C48—C47—H47A109.1
C4—C5B—H5D106.9C46—C47—H47B109.1
H5C—C5B—H5D106.7C48—C47—H47B109.1
C7B—C6B—C5B108.7 (17)H47A—C47—H47B107.8
C7B—C6B—H6C110.0C49—C48—C47113.5 (2)
C5B—C6B—H6C110.0C49—C48—H48A108.9
C7B—C6B—H6D110.0C47—C48—H48A108.9
C5B—C6B—H6D110.0C49—C48—H48B108.9
H6C—C6B—H6D108.3C47—C48—H48B108.9
C6B—C7B—H7C110.4H48A—C48—H48B107.7
C6B—C7B—H7D110.4C50—C49—C48125.7 (2)
H7C—C7B—H7D108.6C50—C49—Rh173.44 (14)
C4—C9—C10119.4 (2)C48—C49—Rh1107.23 (16)
C4—C9—C8119.9 (2)C50—C49—H49115.4 (19)
C10—C9—C8120.74 (19)C48—C49—H49116.6 (19)
C1—C10—C9120.87 (19)Rh1—C49—H49104.5 (19)
C1—C10—C11122.90 (19)C49—C50—C51125.6 (2)
C9—C10—C11116.23 (19)C49—C50—Rh171.11 (14)
C20—C11—C12120.72 (19)C51—C50—Rh1112.22 (17)
C20—C11—C10120.65 (18)C49—C50—H50116 (2)
C12—C11—C10118.29 (19)C51—C50—H50115 (2)
C17—C12—C11119.5 (2)Rh1—C50—H50103 (2)
C17—C12—C13120.2 (2)C50—C51—C52112.5 (2)
C11—C12—C13120.22 (19)C50—C51—H51A109.1
C12—C13—C14114.2 (2)C52—C51—H51A109.1
C12—C13—H13A108.7C50—C51—H51B109.1
C14—C13—H13A108.7C52—C51—H51B109.1
C12—C13—H13B108.7H51A—C51—H51B107.8
C14—C13—H13B108.7C45—C52—C51112.7 (2)
H13A—C13—H13B107.6C45—C52—H52A109.0
C15—C14—C13110.8 (2)C51—C52—H52A109.0
C15—C14—H14A109.5C45—C52—H52B109.0
C13—C14—H14A109.5C51—C52—H52B109.0
C15—C14—H14B109.5H52A—C52—H52B107.8
C13—C14—H14B109.5F2—B1—F3114.7 (11)
H14A—C14—H14B108.1F2—B1—F1113.0 (13)
C14—C15—C16109.6 (2)F3—B1—F1105.9 (12)
C14—C15—H15A109.8F2—B1—F4108.8 (10)
C16—C15—H15A109.8F3—B1—F4106.7 (9)
C14—C15—H15B109.8F1—B1—F4107.2 (10)
C16—C15—H15B109.8F4'—B1'—F3'111.5 (10)
H15A—C15—H15B108.2F4'—B1'—F1'109.2 (9)
C17—C16—C15112.8 (2)F3'—B1'—F1'113.5 (10)
C17—C16—H16A109.0F4'—B1'—F2'108.1 (9)
C15—C16—H16A109.0F3'—B1'—F2'107.5 (8)
C17—C16—H16B109.0F1'—B1'—F2'106.9 (9)
C15—C16—H16B109.0C71—O71—H71109.5
H16A—C16—H16B107.8O71—C71—H71A109.5
C18—C17—C12118.9 (2)O71—C71—H71B109.5
C18—C17—C16118.9 (2)H71A—C71—H71B109.5
C12—C17—C16122.1 (2)O71—C71—H71C109.5
C19—C18—C17121.4 (2)H71A—C71—H71C109.5
C19—C18—H18119.3H71B—C71—H71C109.5
C17—C18—H18119.3C61—O61—H61109.5
C18—C19—C20120.5 (2)O61—C61—H61A109.4
C18—C19—H19119.8O61—C61—H61B109.4
C20—C19—H19119.8H61A—C61—H61B109.5
C19—C20—C11118.4 (2)O61—C61—H61C109.6
C19—C20—P2120.77 (17)H61A—C61—H61C109.5
C11—C20—P2120.64 (16)H61B—C61—H61C109.5
C22—C21—C26118.2 (2)H73A—C73—H73B109.5
C22—C21—P1121.81 (17)H73A—C73—H73C109.5
C26—C21—P1119.56 (16)H73B—C73—H73C109.5
C21—C22—C23120.2 (2)C76—C75—H75A107.6
C21—C22—H22119.9C76—C75—H75B107.6
C23—C22—H22119.9H75A—C75—H75B107.0
C24—C23—C22120.7 (3)C77—C76—C75101.4 (12)
C24—C23—H23119.7C77—C76—H76A111.5
C22—C23—H23119.7C75—C76—H76A111.5
C25—C24—C23119.5 (3)C77—C76—H76B111.5
C25—C24—H24120.2C75—C76—H76B111.5
C23—C24—H24120.2H76A—C76—H76B109.3
C24—C25—C26120.4 (3)C76—C77—H77A109.5
C24—C25—H25119.8C76—C77—H77B109.5
C26—C25—H25119.8H77A—C77—H77B109.5
C25—C26—C21120.9 (2)C76—C77—H77C109.5
C25—C26—H26119.6H77A—C77—H77C109.5
C21—C26—H26119.6H77B—C77—H77C109.5
C27—P1—C1—C2135.31 (19)C27—P1—C21—C2212.0 (3)
C21—P1—C1—C224.2 (2)C1—P1—C21—C22124.7 (2)
Rh1—P1—C1—C2101.12 (18)Rh1—P1—C21—C22108.2 (2)
C27—P1—C1—C1055.60 (19)C27—P1—C21—C26175.6 (2)
C21—P1—C1—C10166.69 (17)C1—P1—C21—C2662.9 (2)
Rh1—P1—C1—C1067.97 (18)Rh1—P1—C21—C2664.2 (2)
C10—C1—C2—C34.6 (3)C26—C21—C22—C231.3 (4)
P1—C1—C2—C3164.83 (19)P1—C21—C22—C23173.9 (2)
C1—C2—C3—C41.1 (4)C21—C22—C23—C241.1 (5)
C2—C3—C4—C93.4 (4)C22—C23—C24—C251.6 (5)
C2—C3—C4—C5177.3 (10)C23—C24—C25—C260.5 (5)
C2—C3—C4—C5B173 (3)C24—C25—C26—C213.0 (4)
C3—C4—C5—C6157.3 (8)C22—C21—C26—C253.4 (4)
C9—C4—C5—C621.9 (19)P1—C21—C26—C25176.1 (2)
C5B—C4—C5—C650 (22)C21—P1—C27—C28122.0 (2)
C4—C5—C6—C750.7 (15)C1—P1—C27—C28126.73 (19)
C5—C6—C7—C864.2 (8)Rh1—P1—C27—C280.1 (2)
C6—C7—C8—C944.7 (4)C21—P1—C27—C3258.0 (2)
C3—C4—C5B—C6B180 (3)C1—P1—C27—C3253.3 (2)
C9—C4—C5B—C6B4 (6)Rh1—P1—C27—C32179.87 (18)
C5—C4—C5B—C6B150 (28)C32—C27—C28—C292.5 (4)
C4—C5B—C6B—C7B32 (5)P1—C27—C28—C29177.6 (2)
C3—C4—C9—C104.2 (3)C27—C28—C29—C301.3 (4)
C5—C4—C9—C10176.6 (11)C28—C29—C30—C310.6 (5)
C5B—C4—C9—C10173 (3)C29—C30—C31—C321.4 (5)
C3—C4—C9—C8175.8 (2)C28—C27—C32—C311.7 (4)
C5—C4—C9—C83.3 (11)P1—C27—C32—C31178.4 (2)
C5B—C4—C9—C87 (3)C30—C31—C32—C270.3 (4)
C7—C8—C9—C414.8 (3)C39—P2—C33—C347.8 (2)
C7—C8—C9—C10165.2 (2)C20—P2—C33—C34119.89 (19)
C2—C1—C10—C93.7 (3)Rh1—P2—C33—C34110.98 (18)
P1—C1—C10—C9165.56 (16)C39—P2—C33—C38178.27 (18)
C2—C1—C10—C11175.3 (2)C20—P2—C33—C3866.1 (2)
P1—C1—C10—C1115.4 (3)Rh1—P2—C33—C3863.00 (19)
C4—C9—C10—C10.6 (3)C38—C33—C34—C351.0 (3)
C8—C9—C10—C1179.4 (2)P2—C33—C34—C35174.93 (19)
C4—C9—C10—C11179.74 (19)C33—C34—C35—C360.1 (4)
C8—C9—C10—C110.3 (3)C34—C35—C36—C370.5 (4)
C1—C10—C11—C2083.5 (3)C35—C36—C37—C380.2 (4)
C9—C10—C11—C2097.4 (2)C36—C37—C38—C330.7 (4)
C1—C10—C11—C12103.2 (2)C34—C33—C38—C371.3 (4)
C9—C10—C11—C1275.9 (2)P2—C33—C38—C37175.47 (19)
C20—C11—C12—C173.1 (3)C33—P2—C39—C4457.7 (2)
C10—C11—C12—C17170.3 (2)C20—P2—C39—C4452.3 (2)
C20—C11—C12—C13178.8 (2)Rh1—P2—C39—C44177.79 (17)
C10—C11—C12—C137.8 (3)C33—P2—C39—C40122.44 (18)
C17—C12—C13—C1416.9 (3)C20—P2—C39—C40127.50 (18)
C11—C12—C13—C14165.0 (2)Rh1—P2—C39—C402.4 (2)
C12—C13—C14—C1545.3 (3)C44—C39—C40—C410.5 (3)
C13—C14—C15—C1662.5 (3)P2—C39—C40—C41179.70 (18)
C14—C15—C16—C1750.2 (3)C39—C40—C41—C421.0 (4)
C11—C12—C17—C184.2 (3)C40—C41—C42—C431.4 (4)
C13—C12—C17—C18173.9 (2)C41—C42—C43—C440.3 (4)
C11—C12—C17—C16176.4 (2)C42—C43—C44—C391.3 (4)
C13—C12—C17—C165.6 (3)C40—C39—C44—C431.6 (3)
C15—C16—C17—C18156.8 (2)P2—C39—C44—C43178.55 (19)
C15—C16—C17—C1222.6 (3)C52—C45—C46—C475.0 (4)
C12—C17—C18—C196.8 (4)Rh1—C45—C46—C47105.3 (2)
C16—C17—C18—C19173.7 (2)C52—C45—C46—Rh1100.3 (3)
C17—C18—C19—C202.0 (4)C45—C46—C47—C4894.6 (3)
C18—C19—C20—C115.3 (3)Rh1—C46—C47—C4810.6 (3)
C18—C19—C20—P2169.38 (19)C46—C47—C48—C4936.2 (3)
C12—C11—C20—C197.8 (3)C47—C48—C49—C5039.1 (4)
C10—C11—C20—C19165.4 (2)C47—C48—C49—Rh142.6 (3)
C12—C11—C20—P2166.86 (16)C48—C49—C50—C514.7 (4)
C10—C11—C20—P219.9 (3)Rh1—C49—C50—C51104.3 (3)
C39—P2—C20—C19123.92 (19)C48—C49—C50—Rh199.6 (2)
C33—P2—C20—C1913.1 (2)C49—C50—C51—C5296.5 (3)
Rh1—P2—C20—C19111.57 (17)Rh1—C50—C51—C5214.4 (3)
C39—P2—C20—C1161.52 (19)C46—C45—C52—C5137.7 (4)
C33—P2—C20—C11172.33 (17)Rh1—C45—C52—C5143.2 (3)
Rh1—P2—C20—C1162.99 (18)C50—C51—C52—C4538.7 (4)
Selected distances (Å) and angles (°) of the rhodium/H8-BINAP cod complexes (CM = centroids of the double bonds of the olefin) top
ComplexRh—PRh—CMP—Rh—PCM—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, 2.3372.143, 2.24590.5884.66
 

References

First citationBruker (2013). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationBruker (2014). APEX2 and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationDrexler, H.-J., Preetz, A., Schmidt, T. & Heller, D. (2007). Handbook of Homogeneous Hydrogenation, edited by J. G. de Vries & C. J. Elsevier, pp. 257–293. Weinheim: Wiley-VCH.  Google Scholar
First citationMeissner, A., Alberico, E., Drexler, H.-J., Baumann, W. & Heller, D. (2014). Catal. Sci. Technol. 4, 3409–3425.  CAS Google Scholar
First citationMiyashita, A., Yasuda, A., Takaya, H., Toriumi, K., Ito, T., Souchi, T. & Noyori, R. (1980). J. Am. Chem. Soc. 102, 7932–7934.  CSD CrossRef CAS Web of Science Google Scholar
First citationParsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationPreetz, A., Drexler, H.-J., Schulz, S. & Heller, D. (2010). Tetrahedron Asymmetry, 21, 1226–1231.  Web of Science CSD CrossRef CAS Google Scholar
First citationPreetz, A., Fischer, C., Kohrt, C., Drexler, H.-J., Baumann, W. & Heller, D. (2011). Organometallics, 30, 5155–5159.  Web of Science CSD CrossRef CAS Google Scholar
First citationSchrock, R. R. & Osborn, J. A. (1971). J. Am. Chem. Soc. 93, 2397–2407.  CrossRef Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (2015). Acta Cryst. C71, 3–8.  Web of Science CrossRef IUCr Journals Google Scholar
First citationShibata, T., Kurakawa, H. & Kanda, K. (2007). J. Org. Chem. 72, 6521–6525.  Web of Science CSD CrossRef PubMed CAS Google Scholar
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationZhang, X., Mashima, K., Koyano, K., Sayo, N., Kumobayashi, H., Akutagawa, S. & Takaya, H. (1994). J. Chem. Soc. Perkin Trans. 1, pp. 2309–2322.  CSD CrossRef Web of Science 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.

Journal logoIUCrDATA
ISSN: 2414-3146
Follow IUCr Journals
Sign up for e-alerts
Follow IUCr on Twitter
Follow us on facebook
Sign up for RSS feeds

[# https x2 cm 20170801 %]