A binuclear rhodium(I) complex with two tetraphosphine ligands at 100 K

Bis(μ-3,11-diethyl-6,8-di­phenyl-3,6,8,11-tetraphosphatri­dec­ane-κ⁴P³,P⁶:P⁸,P¹¹)­dirhodium(I) bis­(tetra­fluoro­borate), [Rh₂(C₂₅H₄₀P₄)₂](BF₄)₂, is a bimetallic complex containing two binucleating tetra-tertiary phosphine ligands. The distance between the metal centers is 5.4555 (11) Å, with no metal–metal bond. The Rh—P bond distances range from 2.2483 (14) to 2.3295 (14) Å. The geometry about the Rh^I atoms is tetrahedrally distorted square planar and the dihedral angle between the two coordination planes is 66.28 (5)°.

S1. Comment

The most frequently used homogeneous catalytic process for producing aldehydes is hydroformylation. Current production exceeds twelve billion pounds annually. The capability for two or more metal centers to work together in heterogeneous reactions is common and has been well documented (George, 1995; Somorjai, 1992; Walther, 1989). However, the ability for two or more metal centers to cooperate in homogeneous catalytic processes is less well documented or understood (Adams et al., 1994; Tsubouchi & Bruce, 1994; Zhang et al., 1988; Collman et al., 1983; Don & Richman, 1992; Hidai et al., 1986; Suss-Fink & Herrmann, 1985). A focus of our research involves the use of a novel catalyst which contains two rhodium centers with a binucleating tetra-tertiary phosphine ligand (Broussard et al., 1993). One objective of this project is to improve the characterization of our novel hydroformylation catalyst, [Rh₂(nbd)₂(racemic-et,ph-P4)](BF₄)₂ [nbd = norbornadiene; et,ph-P4 = (Et₂PCH₂CH₂)(Ph)PCH₂P(Ph)(CH₂CH₂PEt₂)], by using ³¹P{¹H}NMR to monitor possible side reactions which might occur during catalytic cycles. The reported complex was the first resulting from attempted synthesis of possible by-products. The ligand (et,ph-P4) exists as meso and racemic diastereomers, leading to a number of possible isomers for complexes. We report here the structure of the [Rh₂(R,R-et,ph-P4 and S,S-et,ph-P4)](BF₄)₂ isomer complexed with rhodium, (I). \scheme

As shown in Fig. 1, we have successfully synthesized an analog of our novel hydroformylation catalyst containing two et,ph-P4 ligands rather than only one. This new compound, (I), contains two Rh atoms and two binucleating tetra-tertiary phosphine ligands, (R,R-et,ph-P4 and S,S-et,ph-P4), with two BF₄^-. The intramolecular distance between the two Rh^I centers is 5.4555 (11) Å, precluding any direct metal-metal bonding.

The geometry about the Rh atoms is tetrahedrally distorted square planar. A least-squares plane was calculated for each RhP₄ group and these results showed that each Rh atom is essentially in the plane, with deviations of 0.0014 (6) for Rh1 and -0.0069 (6) Å for Rh2. The four P atoms attached to Rh1 are out of the plane with deviations of 0.2702 (7) for P1, 0.2686 (7) for P6, -0.2626 (7) for P2 and -0.2694 (7) Å for P4. Similar results were obtained for the P atoms attached to Rh2, with deviations of 0.2801 (7) for P5, 0.3104 (8) for P7, -0.2749 (7) for P3 and -0.3169 (8) Å for P8. The distortion about each Rh center is presumably due to the five-membered chelate rings. The two coordination planes form a dihedral angle of 66.28 (5)°.

We have also obtained preliminary results for a poor crystal of [Rh₂(meso-et,ph-P4)₂](PF₆)₂. It is orthorhombic, space group Fdd2, with a = 29.316 (6), b = 29.937 (6), c = 28.099 (6) Å and Z = 16 at 100 K. The distance between the Rh^I atoms is somewhat shorter, at 4.771 (2) Å. Efforts to produce better crystals are underway.

Spectroscopic data (³¹P{¹H}NMR) of the reported compound do not correspond with those of unidentified byproducts observed in the catalytic cycle. The crystal structure reported here, along with elemental analysis, have allowed us to identify compound (I) unambiguously and to rule it out as a possible byproduct of the catalytic cycle.

S2. Experimental

All procedures, unless otherwise stated, were conducted in a nitrogen atmosphere using standard Schlenk line or glovebox techniques. [Rh(nbd)₂]BF₄ was prepared according to a modification (Broussard, 1993) of published literature procedures (Schrock & Osborn, 1971; Green et al., 1971), while racemic-et,ph-P4 was prepared according to published procedures (Broussard et al., 1993). [Rh₂(et,ph-P4)₂](BF₄)₂ was prepared by adding [Rh(nbd)₂]BF₄ (0.157 g, 0.420 mmol) and dichloromethane (12 ml) to a 100 ml Schlenk flask. To a second 100 ml Schlenk flask were added racemic-et,ph-P4 ligand (0.199 g, 0.430 mmol) and dichloromethane (12 ml). The rhodium solution was added dropwise, via cannula, to the ligand solution. After stirring overnight (17 h), the solvent was removed under vacuum and the residue brought into a glovebox. The residue was re-dissolved in a minimum volume of dichloromethane and washed with an equal volume of anhydrous diethyl ether, yielding a dark red oil and an opaque yellow suspension. The yellow opaque layer was decanted into a 60 ml frit and filtered, yielding yellow solids. Crystals of (I) were obtained from the yellow solids by slow evaporation from a solution in a mixture of dichloromethane and methanol.

S3. Refinement

Systematic absences were consistent with Cc and C2/c; however, no inversion centers are present in the structure. The absolute structure was determined by refinement of the Flack parameter (Flack, 1983). The deepest hole (-1.03 e Å^-3) is 0.84 Å from Rh2. H atoms were placed in calculated positions with assumed C—H bond distances of 0.930 Å and with U_iso = 1.2U_eq of the attached C atom, and thereafter treated as riding. A torsional parameter for each methyl group was refined. Refinement of the inverted structure led to a Flack parameter of 1.02 (4).

Computing details

Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf-Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996; Farrugia, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1998).

Figures

Fig. 1. The molecular structure of (I) showing the numbering scheme and with displacement ellipsoids at the 50% probability level. H atoms are not shown.

Bis(µ-3,11-diethyl-6,8-diphenyl-3,6,8,11-tetraphosphatridecane- κ⁴-P³,P⁶:P⁸,P¹¹)dirhodium(I) bis(tetrafluoroborate)

Crystal data

[Rh2(C25H40P4)2](BF4)2	Dx = 1.516 Mg m^−3
Mr = 1308.3	Melting point: not measured K
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
a = 15.651 (3) Å	Cell parameters from 25 reflections
b = 16.048 (3) Å	θ = 10.7–20.8°
c = 24.022 (5) Å	µ = 0.86 mm^−1
β = 108.18 (3)°	T = 100 K
V = 5732 (2) Å^3	Prism, yellow
Z = 4	0.48 × 0.25 × 0.23 mm
F(000) = 2688

Data collection

Enraf-Nonius CAD-4 (with Oxford Cryostream cooler) diffractometer	7681 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.000
Graphite monochromator	θmax = 30.0°, θmin = 2.5°
ω/2θ scans	h = −20→22
Absorption correction: ψ-scan (North, et al., 1968)	k = 0→22
Tmin = 0.640, Tmax = 0.821	l = −33→0
8531 measured reflections	3 standard reflections every 60 min
8531 independent reflections	intensity decay: 1.0%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.038	H-atom parameters constrained
wR(F^2) = 0.095	w = 1/[σ^2(Fo^2) + (0.0505P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.05
8531 reflections	Δρmax = 0.73 e Å^−3
631 parameters	Δρmin = −1.03 e Å^−3
2 restraints	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.02 (2)

Special details

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 on F² for ALL reflections except for 0 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating _R_factor_obs 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Rh1	0.54137 (2)	0.34163 (2)	0.433019 (16)	0.01582 (8)
Rh2	0.49355 (2)	0.21265 (2)	0.631330 (16)	0.01651 (8)
P1	0.68098 (9)	0.40179 (8)	0.45212 (6)	0.0194 (2)
P2	0.53823 (10)	0.27803 (9)	0.34642 (6)	0.0225 (3)
P3	0.52431 (9)	0.15659 (8)	0.55018 (6)	0.0183 (2)
P4	0.53025 (8)	0.42893 (8)	0.50463 (5)	0.0152 (2)
P5	0.47600 (8)	0.35384 (8)	0.61483 (5)	0.0162 (2)
P6	0.42383 (8)	0.25882 (8)	0.42929 (5)	0.0164 (2)
P7	0.54240 (10)	0.08381 (8)	0.67262 (6)	0.0211 (3)
P8	0.42932 (10)	0.24182 (8)	0.70304 (6)	0.0226 (3)
B1	0.4444 (6)	−0.0356 (5)	0.3715 (3)	0.0340 (15)
B2	0.5631 (6)	0.2241 (4)	0.1523 (3)	0.0324 (15)
F1	0.4927 (6)	−0.0269 (6)	0.4289 (2)	0.145 (4)
F2	0.4046 (5)	−0.1123 (3)	0.3620 (4)	0.097 (3)
F3	0.5041 (3)	−0.0294 (3)	0.3398 (2)	0.0542 (11)
F4	0.3808 (2)	0.0263 (2)	0.3583 (2)	0.0400 (9)
F5	0.5415 (3)	0.3073 (2)	0.1398 (2)	0.0439 (10)
F6	0.4957 (3)	0.1872 (3)	0.1698 (2)	0.0531 (12)
F7	0.5705 (3)	0.1861 (3)	0.10235 (18)	0.0499 (11)
F8	0.6436 (3)	0.2183 (3)	0.19724 (18)	0.0541 (13)
C''	0.4568 (3)	0.1619 (3)	0.4716 (2)	0.0191 (9)
H''1	0.4889	0.1290	0.4507	0.023*
H''2	0.4013	0.1323	0.4680	0.023*
C'	0.4539 (3)	0.4198 (3)	0.5491 (2)	0.0160 (8)
H'1	0.3963	0.4020	0.5226	0.019*
H'2	0.4451	0.4760	0.5613	0.019*
C1	0.3746 (4)	0.2183 (4)	0.3540 (2)	0.0238 (11)
H1A	0.3402	0.1683	0.3548	0.029*
H1B	0.3340	0.2595	0.3301	0.029*
C2	0.4488 (4)	0.1983 (3)	0.3268 (2)	0.0260 (11)
H2A	0.4231	0.1956	0.2845	0.031*
H2B	0.4746	0.1443	0.3406	0.031*
C3	0.7004 (3)	0.4754 (3)	0.5143 (2)	0.0212 (10)
H3A	0.7638	0.4756	0.5369	0.025*
H3B	0.6839	0.5312	0.4995	0.025*
C4	0.6450 (3)	0.4503 (3)	0.5538 (2)	0.0196 (9)
H4A	0.6441	0.4950	0.5807	0.023*
H4B	0.6702	0.4010	0.5762	0.023*
C5	0.7669 (4)	0.3213 (4)	0.4780 (3)	0.0299 (12)
H5A	0.7488	0.2853	0.5048	0.036*
H5B	0.7676	0.2875	0.4447	0.036*
C6	0.8634 (4)	0.3508 (5)	0.5090 (4)	0.050 (2)
H6A	0.9023	0.3034	0.5207	0.075*
H6B	0.8647	0.3828	0.5430	0.075*
H6C	0.8837	0.3848	0.4827	0.075*
C7	0.7199 (4)	0.4610 (4)	0.3998 (3)	0.0296 (12)
H7A	0.7806	0.4805	0.4193	0.036*
H7B	0.7222	0.4242	0.3683	0.036*
C8	0.6611 (5)	0.5355 (4)	0.3737 (3)	0.0340 (13)
H8A	0.6854	0.5637	0.3468	0.051*
H8B	0.6594	0.5730	0.4045	0.051*
H8C	0.6012	0.5167	0.3533	0.051*
C9	0.5102 (5)	0.3491 (4)	0.2831 (3)	0.0333 (14)
H9A	0.5571	0.3909	0.2899	0.040*
H9B	0.5104	0.3176	0.2487	0.040*
C10	0.4205 (6)	0.3930 (5)	0.2701 (3)	0.0466 (18)
H10A	0.4117	0.4287	0.2367	0.070*
H10B	0.4199	0.4257	0.3034	0.070*
H10C	0.3732	0.3524	0.2619	0.070*
C11	0.6341 (4)	0.2229 (4)	0.3341 (3)	0.0313 (13)
H11A	0.6162	0.2029	0.2940	0.038*
H11B	0.6830	0.2621	0.3388	0.038*
C12	0.6682 (5)	0.1500 (4)	0.3749 (3)	0.0372 (14)
H12A	0.7182	0.1247	0.3662	0.056*
H12B	0.6210	0.1098	0.3697	0.056*
H12C	0.6873	0.1692	0.4147	0.056*
C13	0.3220 (3)	0.2935 (3)	0.4439 (2)	0.0200 (9)
C14	0.2779 (4)	0.3631 (4)	0.4124 (3)	0.0271 (11)
H14	0.3012	0.3889	0.3856	0.033*
C15	0.2000 (4)	0.3938 (4)	0.4207 (3)	0.0357 (14)
H15	0.1721	0.4406	0.4002	0.043*
C16	0.1637 (4)	0.3545 (5)	0.4596 (3)	0.0394 (16)
H16	0.1110	0.3745	0.4648	0.047*
C17	0.2060 (4)	0.2860 (5)	0.4904 (3)	0.0371 (15)
H17	0.1812	0.2593	0.5161	0.044*
C18	0.2856 (4)	0.2564 (4)	0.4837 (3)	0.0282 (12)
H18	0.3147	0.2113	0.5059	0.034*
C19	0.4956 (3)	0.5322 (3)	0.4732 (2)	0.0164 (9)
C20	0.4474 (4)	0.5397 (3)	0.4136 (2)	0.0231 (10)
H20	0.4318	0.4921	0.3906	0.028*
C21	0.4229 (4)	0.6174 (4)	0.3886 (3)	0.0288 (12)
H21	0.3906	0.6217	0.3490	0.035*
C22	0.4463 (4)	0.6891 (4)	0.4226 (3)	0.0289 (12)
H22	0.4301	0.7413	0.4058	0.035*
C23	0.4941 (4)	0.6821 (3)	0.4818 (3)	0.0263 (11)
H23	0.5103	0.7298	0.5046	0.032*
C24	0.5178 (4)	0.6044 (3)	0.5070 (2)	0.0230 (10)
H24	0.5487	0.6003	0.5468	0.028*
C25	0.5707 (3)	0.4105 (3)	0.6660 (2)	0.0173 (9)
C26	0.5677 (4)	0.4965 (3)	0.6726 (2)	0.0205 (10)
H26	0.5159	0.5259	0.6529	0.025*
C27	0.6436 (4)	0.5392 (3)	0.7094 (2)	0.0231 (10)
H27	0.6421	0.5967	0.7134	0.028*
C28	0.7194 (4)	0.4955 (4)	0.7390 (2)	0.0285 (12)
H28	0.7694	0.5235	0.7630	0.034*
C29	0.7217 (4)	0.4098 (4)	0.7335 (2)	0.0281 (12)
H29	0.7731	0.3804	0.7540	0.034*
C30	0.6470 (4)	0.3672 (4)	0.6972 (2)	0.0230 (10)
H30	0.6486	0.3095	0.6940	0.028*
C31	0.6431 (4)	0.1602 (3)	0.5533 (2)	0.0232 (10)
C32	0.6785 (4)	0.1071 (4)	0.5204 (3)	0.0335 (13)
H32	0.6399	0.0750	0.4909	0.040*
C33	0.7706 (5)	0.1012 (5)	0.5310 (3)	0.0421 (17)
H33	0.7934	0.0657	0.5085	0.051*
C34	0.8275 (5)	0.1474 (5)	0.5743 (3)	0.0421 (18)
H34	0.8892	0.1420	0.5817	0.050*
C35	0.7958 (4)	0.2023 (4)	0.6078 (3)	0.0355 (14)
H35	0.8351	0.2344	0.6369	0.043*
C36	0.7019 (4)	0.2079 (4)	0.5961 (3)	0.0266 (11)
H36	0.6791	0.2447	0.6178	0.032*
C37	0.5130 (4)	0.0431 (3)	0.5576 (2)	0.0253 (11)
H37A	0.4507	0.0288	0.5519	0.030*
H37B	0.5326	0.0141	0.5283	0.030*
C38	0.5716 (4)	0.0170 (3)	0.6193 (3)	0.0279 (12)
H38A	0.6348	0.0234	0.6230	0.033*
H38B	0.5606	−0.0409	0.6263	0.033*
C39	0.3791 (4)	0.3885 (3)	0.6384 (2)	0.0229 (10)
H39A	0.3775	0.4488	0.6400	0.028*
H39B	0.3231	0.3693	0.6107	0.028*
C40	0.3903 (4)	0.3518 (3)	0.6989 (3)	0.0268 (12)
H40A	0.3333	0.3542	0.7069	0.032*
H40B	0.4337	0.3846	0.7284	0.032*
C41	0.6483 (4)	0.0923 (4)	0.7337 (3)	0.0316 (13)
H41A	0.6898	0.1266	0.7211	0.038*
H41B	0.6359	0.1210	0.7659	0.038*
C42	0.6950 (5)	0.0086 (4)	0.7568 (3)	0.0471 (19)
H42A	0.7490	0.0191	0.7885	0.071*
H42B	0.7099	−0.0196	0.7258	0.071*
H42C	0.6553	−0.0256	0.7704	0.071*
C43	0.4737 (4)	0.0133 (3)	0.7012 (3)	0.0266 (11)
H43A	0.5096	−0.0348	0.7186	0.032*
H43B	0.4568	0.0418	0.7318	0.032*
C44	0.3895 (4)	−0.0161 (4)	0.6549 (3)	0.0373 (15)
H44A	0.3564	−0.0524	0.6724	0.056*
H44B	0.4057	−0.0456	0.6249	0.056*
H44C	0.3530	0.0311	0.6379	0.056*
C45	0.3254 (4)	0.1841 (4)	0.6937 (3)	0.0309 (13)
H45A	0.3403	0.1266	0.7051	0.037*
H45B	0.2953	0.2072	0.7199	0.037*
C46	0.2594 (4)	0.1856 (4)	0.6305 (3)	0.0367 (14)
H46A	0.2067	0.1540	0.6290	0.055*
H46B	0.2880	0.1617	0.6043	0.055*
H46C	0.2427	0.2422	0.6192	0.055*
C47	0.4849 (5)	0.2273 (4)	0.7816 (3)	0.0303 (12)
H47A	0.4430	0.2428	0.8022	0.036*
H47B	0.4983	0.1686	0.7888	0.036*
C48	0.5716 (5)	0.2764 (4)	0.8076 (3)	0.0402 (16)
H48A	0.5952	0.2651	0.8489	0.060*
H48B	0.5593	0.3349	0.8017	0.060*
H48C	0.6148	0.2601	0.7888	0.060*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Rh1	0.01687 (16)	0.01697 (16)	0.01341 (16)	0.00120 (14)	0.00442 (13)	−0.00025 (14)
Rh2	0.02153 (18)	0.01374 (15)	0.01414 (16)	−0.00037 (14)	0.00540 (14)	0.00016 (14)
P1	0.0179 (6)	0.0212 (6)	0.0200 (6)	0.0010 (5)	0.0073 (5)	−0.0003 (5)
P2	0.0271 (7)	0.0246 (6)	0.0168 (6)	−0.0011 (5)	0.0084 (5)	−0.0024 (5)
P3	0.0223 (6)	0.0162 (6)	0.0158 (6)	0.0040 (5)	0.0048 (5)	0.0007 (4)
P4	0.0150 (5)	0.0161 (5)	0.0138 (5)	0.0011 (4)	0.0034 (4)	−0.0002 (4)
P5	0.0189 (6)	0.0142 (5)	0.0158 (6)	0.0008 (4)	0.0059 (5)	0.0002 (4)
P6	0.0162 (6)	0.0173 (5)	0.0136 (5)	0.0007 (4)	0.0016 (5)	−0.0006 (4)
P7	0.0285 (7)	0.0151 (5)	0.0167 (6)	−0.0001 (5)	0.0027 (5)	0.0017 (5)
P8	0.0325 (7)	0.0180 (6)	0.0205 (6)	−0.0029 (5)	0.0130 (6)	−0.0002 (5)
B1	0.049 (4)	0.032 (3)	0.021 (3)	0.008 (3)	0.013 (3)	0.003 (3)
B2	0.044 (4)	0.024 (3)	0.023 (3)	−0.001 (3)	0.002 (3)	−0.001 (2)
F1	0.191 (8)	0.180 (8)	0.024 (3)	0.150 (7)	−0.023 (4)	−0.024 (3)
F2	0.143 (6)	0.027 (2)	0.173 (7)	−0.004 (3)	0.124 (6)	−0.012 (3)
F3	0.045 (2)	0.058 (3)	0.062 (3)	−0.004 (2)	0.020 (2)	−0.006 (2)
F4	0.0273 (18)	0.0305 (19)	0.056 (3)	0.0017 (15)	0.0038 (18)	0.0073 (18)
F5	0.059 (3)	0.0238 (17)	0.052 (3)	−0.0063 (17)	0.022 (2)	−0.0048 (17)
F6	0.044 (2)	0.046 (2)	0.065 (3)	−0.015 (2)	0.011 (2)	0.009 (2)
F7	0.077 (3)	0.034 (2)	0.033 (2)	0.005 (2)	0.009 (2)	−0.0079 (18)
F8	0.038 (2)	0.092 (4)	0.026 (2)	−0.010 (2)	0.0012 (18)	0.015 (2)
C''	0.021 (2)	0.019 (2)	0.017 (2)	0.0001 (18)	0.0057 (19)	−0.0011 (18)
C'	0.015 (2)	0.017 (2)	0.014 (2)	0.0027 (16)	0.0029 (17)	0.0002 (16)
C1	0.023 (3)	0.028 (3)	0.014 (2)	−0.003 (2)	−0.004 (2)	−0.0025 (19)
C2	0.033 (3)	0.025 (3)	0.021 (3)	−0.006 (2)	0.009 (2)	−0.009 (2)
C3	0.015 (2)	0.023 (2)	0.025 (3)	−0.0029 (18)	0.005 (2)	−0.005 (2)
C4	0.016 (2)	0.024 (2)	0.019 (2)	0.0033 (18)	0.0053 (18)	0.0010 (19)
C5	0.026 (3)	0.030 (3)	0.031 (3)	0.009 (2)	0.005 (2)	0.004 (2)
C6	0.026 (3)	0.051 (4)	0.058 (5)	0.016 (3)	−0.010 (3)	−0.026 (4)
C7	0.033 (3)	0.031 (3)	0.030 (3)	−0.002 (2)	0.017 (3)	0.000 (2)
C8	0.040 (3)	0.030 (3)	0.035 (3)	0.003 (3)	0.016 (3)	0.011 (3)
C9	0.045 (4)	0.036 (3)	0.019 (3)	−0.007 (3)	0.012 (3)	0.000 (2)
C10	0.063 (5)	0.047 (4)	0.028 (3)	0.013 (4)	0.012 (3)	0.008 (3)
C11	0.037 (3)	0.034 (3)	0.028 (3)	0.003 (2)	0.018 (3)	−0.009 (2)
C12	0.038 (3)	0.036 (3)	0.037 (3)	0.001 (3)	0.009 (3)	−0.011 (3)
C13	0.018 (2)	0.023 (2)	0.016 (2)	0.0014 (18)	0.0016 (18)	−0.0010 (18)
C14	0.021 (2)	0.028 (3)	0.029 (3)	0.003 (2)	0.003 (2)	0.001 (2)
C15	0.023 (3)	0.040 (3)	0.041 (4)	0.010 (2)	0.005 (3)	0.000 (3)
C16	0.019 (3)	0.048 (4)	0.051 (4)	0.010 (3)	0.010 (3)	−0.007 (3)
C17	0.022 (3)	0.054 (4)	0.035 (4)	0.003 (3)	0.009 (3)	0.008 (3)
C18	0.022 (3)	0.030 (3)	0.030 (3)	0.004 (2)	0.004 (2)	0.005 (2)
C19	0.016 (2)	0.0133 (19)	0.021 (2)	0.0022 (16)	0.0067 (18)	−0.0005 (17)
C20	0.027 (3)	0.023 (2)	0.019 (2)	0.005 (2)	0.007 (2)	0.003 (2)
C21	0.035 (3)	0.029 (3)	0.023 (3)	0.008 (2)	0.009 (2)	0.006 (2)
C22	0.036 (3)	0.022 (3)	0.032 (3)	0.006 (2)	0.016 (3)	0.008 (2)
C23	0.031 (3)	0.018 (2)	0.034 (3)	0.002 (2)	0.016 (3)	−0.003 (2)
C24	0.023 (2)	0.023 (2)	0.024 (3)	−0.003 (2)	0.009 (2)	−0.004 (2)
C25	0.020 (2)	0.020 (2)	0.011 (2)	0.0003 (18)	0.0028 (17)	0.0026 (17)
C26	0.028 (3)	0.018 (2)	0.016 (2)	0.0022 (19)	0.007 (2)	0.0004 (18)
C27	0.032 (3)	0.020 (2)	0.016 (2)	−0.003 (2)	0.007 (2)	−0.0002 (19)
C28	0.029 (3)	0.034 (3)	0.019 (2)	−0.009 (2)	0.003 (2)	0.001 (2)
C29	0.030 (3)	0.038 (3)	0.015 (2)	0.002 (2)	0.004 (2)	0.005 (2)
C30	0.027 (3)	0.024 (2)	0.016 (2)	0.006 (2)	0.005 (2)	0.0047 (19)
C31	0.022 (2)	0.029 (3)	0.017 (2)	0.011 (2)	0.0038 (19)	0.004 (2)
C32	0.036 (3)	0.037 (3)	0.027 (3)	0.018 (3)	0.009 (3)	0.000 (2)
C33	0.038 (4)	0.048 (4)	0.043 (4)	0.025 (3)	0.016 (3)	0.008 (3)
C34	0.030 (3)	0.054 (4)	0.043 (4)	0.020 (3)	0.014 (3)	0.017 (3)
C35	0.021 (3)	0.049 (4)	0.032 (3)	−0.001 (3)	0.002 (2)	0.006 (3)
C36	0.024 (3)	0.034 (3)	0.023 (3)	0.004 (2)	0.009 (2)	0.008 (2)
C37	0.038 (3)	0.015 (2)	0.020 (2)	0.006 (2)	0.005 (2)	0.0013 (19)
C38	0.044 (3)	0.018 (2)	0.022 (3)	0.005 (2)	0.010 (2)	0.004 (2)
C39	0.023 (2)	0.022 (2)	0.028 (3)	0.0049 (19)	0.013 (2)	0.003 (2)
C40	0.041 (3)	0.022 (2)	0.025 (3)	0.000 (2)	0.021 (2)	0.001 (2)
C41	0.038 (3)	0.024 (3)	0.026 (3)	−0.001 (2)	0.001 (2)	0.001 (2)
C42	0.053 (4)	0.032 (3)	0.034 (3)	0.003 (3)	−0.019 (3)	0.008 (3)
C43	0.036 (3)	0.018 (2)	0.024 (3)	−0.007 (2)	0.008 (2)	−0.001 (2)
C44	0.037 (3)	0.029 (3)	0.046 (4)	−0.008 (3)	0.012 (3)	−0.005 (3)
C45	0.032 (3)	0.033 (3)	0.033 (3)	−0.008 (2)	0.019 (3)	−0.003 (2)
C46	0.034 (3)	0.037 (3)	0.042 (4)	−0.013 (3)	0.017 (3)	−0.001 (3)
C47	0.047 (4)	0.023 (3)	0.023 (3)	−0.004 (2)	0.013 (3)	0.003 (2)
C48	0.065 (5)	0.030 (3)	0.020 (3)	0.001 (3)	0.007 (3)	0.000 (2)

Geometric parameters (Å, º)

Rh1—P6	2.2483 (14)	B2—F6	1.385 (9)
Rh1—P4	2.2670 (13)	B2—F5	1.387 (8)
Rh1—P1	2.3003 (15)	C1—C2	1.534 (8)
Rh1—P2	2.3039 (15)	C3—C4	1.525 (7)
Rh2—P8	2.2973 (15)	C5—C6	1.536 (9)
Rh2—P5	2.3018 (13)	C7—C8	1.519 (8)
Rh2—P7	2.3174 (14)	C9—C10	1.513 (10)
Rh2—P3	2.3295 (14)	C11—C12	1.512 (9)
P1—C7	1.825 (6)	C13—C18	1.390 (8)
P1—C5	1.829 (6)	C13—C14	1.403 (7)
P1—C3	1.854 (5)	C14—C15	1.385 (8)
P2—C9	1.842 (6)	C15—C16	1.388 (10)
P2—C11	1.844 (6)	C16—C17	1.374 (10)
P2—C2	1.845 (6)	C17—C18	1.388 (9)
P3—C31	1.838 (6)	C19—C24	1.395 (7)
P3—C37	1.844 (5)	C19—C20	1.399 (7)
P3—C''	1.856 (5)	C20—C21	1.386 (8)
P4—C19	1.832 (5)	C21—C22	1.392 (9)
P4—C'	1.840 (5)	C22—C23	1.389 (9)
P4—C4	1.847 (5)	C23—C24	1.385 (8)
P5—C'	1.843 (5)	C25—C30	1.383 (7)
P5—C25	1.844 (5)	C25—C26	1.391 (7)
P5—C39	1.862 (5)	C26—C27	1.417 (8)
P6—C13	1.823 (5)	C27—C28	1.370 (8)
P6—C''	1.840 (5)	C28—C29	1.383 (9)
P6—C1	1.850 (5)	C29—C30	1.400 (8)
P7—C38	1.833 (6)	C31—C36	1.380 (8)
P7—C43	1.835 (6)	C31—C32	1.389 (8)
P7—C41	1.844 (6)	C32—C33	1.386 (9)
P8—C45	1.824 (6)	C33—C34	1.359 (11)
P8—C47	1.830 (6)	C34—C35	1.384 (10)
P8—C40	1.860 (6)	C35—C36	1.410 (8)
B1—F1	1.356 (9)	C37—C38	1.538 (8)
B1—F2	1.366 (9)	C39—C40	1.526 (8)
B1—F4	1.371 (8)	C41—C42	1.547 (9)
B1—F3	1.380 (9)	C43—C44	1.510 (9)
B2—F7	1.382 (8)	C45—C46	1.545 (10)
B2—F8	1.383 (9)	C47—C48	1.523 (9)
P6—Rh1—P4	98.05 (5)	F1—B1—F4	107.1 (6)
P6—Rh1—P1	166.04 (5)	F2—B1—F4	110.7 (7)
P4—Rh1—P1	83.24 (5)	F1—B1—F3	107.2 (8)
P6—Rh1—P2	85.16 (6)	F2—B1—F3	109.0 (6)
P4—Rh1—P2	166.88 (5)	F4—B1—F3	112.8 (6)
P1—Rh1—P2	96.74 (6)	F7—B2—F8	110.2 (6)
P8—Rh2—P5	82.64 (5)	F7—B2—F6	110.7 (6)
P8—Rh2—P7	91.37 (5)	F8—B2—F6	109.1 (6)
P5—Rh2—P7	163.27 (5)	F7—B2—F5	108.5 (5)
P8—Rh2—P3	163.57 (5)	F8—B2—F5	109.6 (6)
P5—Rh2—P3	106.31 (5)	F6—B2—F5	108.7 (6)
P7—Rh2—P3	83.50 (5)	P6—C''—P3	125.0 (3)
C7—P1—C5	103.6 (3)	P4—C'—P5	124.1 (3)
C7—P1—C3	102.6 (3)	C2—C1—P6	110.4 (4)
C5—P1—C3	104.9 (3)	C1—C2—P2	111.2 (4)
C7—P1—Rh1	125.6 (2)	C4—C3—P1	110.5 (3)
C5—P1—Rh1	108.9 (2)	C3—C4—P4	106.3 (3)
C3—P1—Rh1	109.57 (17)	C6—C5—P1	117.0 (5)
C9—P2—C11	99.3 (3)	C8—C7—P1	113.9 (4)
C9—P2—C2	104.6 (3)	C10—C9—P2	115.2 (5)
C11—P2—C2	102.5 (3)	C12—C11—P2	114.1 (4)
C9—P2—Rh1	113.8 (2)	C18—C13—C14	118.2 (5)
C11—P2—Rh1	124.6 (2)	C18—C13—P6	124.9 (4)
C2—P2—Rh1	109.77 (18)	C14—C13—P6	116.9 (4)
C31—P3—C37	98.8 (3)	C15—C14—C13	120.9 (6)
C31—P3—C''	106.7 (2)	C14—C15—C16	119.9 (6)
C37—P3—C''	95.9 (2)	C17—C16—C15	119.8 (6)
C31—P3—Rh2	115.13 (19)	C16—C17—C18	120.6 (6)
C37—P3—Rh2	104.47 (19)	C17—C18—C13	120.6 (6)
C''—P3—Rh2	129.24 (17)	C24—C19—C20	118.8 (5)
C19—P4—C'	98.6 (2)	C24—C19—P4	121.6 (4)
C19—P4—C4	101.5 (2)	C20—C19—P4	119.7 (4)
C'—P4—C4	108.8 (2)	C21—C20—C19	120.5 (5)
C19—P4—Rh1	109.22 (17)	C20—C21—C22	120.2 (5)
C'—P4—Rh1	127.50 (16)	C23—C22—C21	119.5 (5)
C4—P4—Rh1	108.06 (17)	C24—C23—C22	120.4 (5)
C'—P5—C25	100.6 (2)	C23—C24—C19	120.6 (5)
C'—P5—C39	97.8 (2)	C30—C25—C26	119.5 (5)
C25—P5—C39	102.2 (2)	C30—C25—P5	119.4 (4)
C'—P5—Rh2	133.93 (16)	C26—C25—P5	121.1 (4)
C25—P5—Rh2	110.07 (16)	C25—C26—C27	119.9 (5)
C39—P5—Rh2	107.83 (18)	C28—C27—C26	119.9 (5)
C13—P6—C''	105.3 (2)	C27—C28—C29	120.2 (5)
C13—P6—C1	100.0 (2)	C28—C29—C30	120.3 (5)
C''—P6—C1	101.7 (2)	C25—C30—C29	120.2 (5)
C13—P6—Rh1	124.43 (18)	C36—C31—C32	118.2 (5)
C''—P6—Rh1	113.12 (17)	C36—C31—P3	118.6 (4)
C1—P6—Rh1	109.44 (19)	C32—C31—P3	122.4 (5)
C38—P7—C43	101.8 (3)	C33—C32—C31	120.9 (6)
C38—P7—C41	103.9 (3)	C34—C33—C32	119.9 (6)
C43—P7—C41	103.5 (3)	C33—C34—C35	121.6 (6)
C38—P7—Rh2	110.09 (18)	C34—C35—C36	117.7 (6)
C43—P7—Rh2	123.8 (2)	C31—C36—C35	121.6 (6)
C41—P7—Rh2	111.7 (2)	C38—C37—P3	108.4 (4)
C45—P8—C47	100.5 (3)	C37—C38—P7	108.1 (4)
C45—P8—C40	102.1 (3)	C40—C39—P5	108.2 (4)
C47—P8—C40	102.6 (3)	C39—C40—P8	110.8 (4)
C45—P8—Rh2	112.7 (2)	C42—C41—P7	115.4 (4)
C47—P8—Rh2	124.7 (2)	C44—C43—P7	113.3 (4)
C40—P8—Rh2	111.49 (17)	C46—C45—P8	114.2 (4)
F1—B1—F2	110.0 (8)	C48—C47—P8	115.7 (4)
P6—Rh1—P1—C7	145.0 (3)	C'—P4—C4—C3	−168.2 (3)
P4—Rh1—P1—C7	−118.9 (2)	Rh1—P4—C4—C3	49.9 (4)
P2—Rh1—P1—C7	47.9 (2)	C7—P1—C5—C6	60.8 (6)
P6—Rh1—P1—C5	21.7 (3)	C3—P1—C5—C6	−46.4 (6)
P4—Rh1—P1—C5	117.8 (2)	Rh1—P1—C5—C6	−163.6 (5)
P2—Rh1—P1—C5	−75.4 (2)	C5—P1—C7—C8	−177.3 (5)
P6—Rh1—P1—C3	−92.5 (3)	C3—P1—C7—C8	−68.3 (5)
P4—Rh1—P1—C3	3.64 (19)	Rh1—P1—C7—C8	57.2 (5)
P2—Rh1—P1—C3	170.42 (19)	C11—P2—C9—C10	167.1 (5)
P6—Rh1—P2—C9	115.1 (2)	C2—P2—C9—C10	61.5 (6)
P4—Rh1—P2—C9	10.3 (4)	Rh1—P2—C9—C10	−58.3 (6)
P1—Rh1—P2—C9	−78.8 (2)	C9—P2—C11—C12	−172.6 (5)
P6—Rh1—P2—C11	−123.7 (3)	C2—P2—C11—C12	−65.3 (5)
P4—Rh1—P2—C11	131.5 (3)	Rh1—P2—C11—C12	59.8 (5)
P1—Rh1—P2—C11	42.4 (3)	C''—P6—C13—C18	5.7 (5)
P6—Rh1—P2—C2	−1.8 (2)	C1—P6—C13—C18	110.9 (5)
P4—Rh1—P2—C2	−106.6 (3)	Rh1—P6—C13—C18	−127.1 (4)
P1—Rh1—P2—C2	164.3 (2)	C''—P6—C13—C14	−174.4 (4)
P8—Rh2—P3—C31	−153.8 (2)	C1—P6—C13—C14	−69.3 (5)
P5—Rh2—P3—C31	84.8 (2)	Rh1—P6—C13—C14	52.7 (5)
P7—Rh2—P3—C31	−81.3 (2)	C18—C13—C14—C15	−0.2 (9)
P8—Rh2—P3—C37	−46.6 (3)	P6—C13—C14—C15	180.0 (5)
P5—Rh2—P3—C37	−168.0 (2)	C13—C14—C15—C16	−1.4 (10)
P7—Rh2—P3—C37	25.9 (2)	C14—C15—C16—C17	0.9 (11)
P8—Rh2—P3—C''	63.7 (3)	C15—C16—C17—C18	1.0 (11)
P5—Rh2—P3—C''	−57.6 (2)	C16—C17—C18—C13	−2.5 (10)
P7—Rh2—P3—C''	136.2 (2)	C14—C13—C18—C17	2.1 (9)
P6—Rh1—P4—C19	−111.27 (17)	P6—C13—C18—C17	−178.1 (5)
P1—Rh1—P4—C19	82.75 (17)	C'—P4—C19—C24	71.9 (4)
P2—Rh1—P4—C19	−7.9 (3)	C4—P4—C19—C24	−39.4 (5)
P6—Rh1—P4—C'	6.5 (2)	Rh1—P4—C19—C24	−153.3 (4)
P1—Rh1—P4—C'	−159.5 (2)	C'—P4—C19—C20	−109.5 (4)
P2—Rh1—P4—C'	109.9 (3)	C4—P4—C19—C20	139.3 (4)
P6—Rh1—P4—C4	139.12 (18)	Rh1—P4—C19—C20	25.3 (4)
P1—Rh1—P4—C4	−26.86 (18)	C24—C19—C20—C21	0.5 (8)
P2—Rh1—P4—C4	−117.5 (3)	P4—C19—C20—C21	−178.1 (4)
P8—Rh2—P5—C'	−148.0 (2)	C19—C20—C21—C22	0.3 (9)
P7—Rh2—P5—C'	142.3 (3)	C20—C21—C22—C23	−0.3 (9)
P3—Rh2—P5—C'	17.9 (2)	C21—C22—C23—C24	−0.5 (9)
P8—Rh2—P5—C25	83.37 (17)	C22—C23—C24—C19	1.3 (8)
P7—Rh2—P5—C25	13.6 (3)	C20—C19—C24—C23	−1.3 (7)
P3—Rh2—P5—C25	−110.72 (17)	P4—C19—C24—C23	177.3 (4)
P8—Rh2—P5—C39	−27.4 (2)	C'—P5—C25—C30	−131.1 (4)
P7—Rh2—P5—C39	−97.2 (3)	C39—P5—C25—C30	128.4 (4)
P3—Rh2—P5—C39	138.5 (2)	Rh2—P5—C25—C30	14.0 (4)
P4—Rh1—P6—C13	32.0 (2)	C'—P5—C25—C26	47.2 (4)
P1—Rh1—P6—C13	126.3 (3)	C39—P5—C25—C26	−53.3 (5)
P2—Rh1—P6—C13	−135.2 (2)	Rh2—P5—C25—C26	−167.7 (4)
P4—Rh1—P6—C''	−97.76 (18)	C30—C25—C26—C27	2.3 (8)
P1—Rh1—P6—C''	−3.4 (3)	P5—C25—C26—C27	−176.0 (4)
P2—Rh1—P6—C''	95.05 (18)	C25—C26—C27—C28	−0.9 (8)
P4—Rh1—P6—C1	149.6 (2)	C26—C27—C28—C29	−0.5 (8)
P1—Rh1—P6—C1	−116.0 (3)	C27—C28—C29—C30	0.6 (9)
P2—Rh1—P6—C1	−17.5 (2)	C26—C25—C30—C29	−2.3 (8)
P8—Rh2—P7—C38	162.9 (2)	P5—C25—C30—C29	176.1 (4)
P5—Rh2—P7—C38	−128.6 (3)	C28—C29—C30—C25	0.8 (8)
P3—Rh2—P7—C38	−1.5 (2)	C37—P3—C31—C36	−122.4 (5)
P8—Rh2—P7—C43	42.5 (2)	C''—P3—C31—C36	138.7 (4)
P5—Rh2—P7—C43	111.0 (3)	Rh2—P3—C31—C36	−11.8 (5)
P3—Rh2—P7—C43	−121.9 (2)	C37—P3—C31—C32	47.3 (5)
P8—Rh2—P7—C41	−82.2 (2)	C''—P3—C31—C32	−51.6 (5)
P5—Rh2—P7—C41	−13.7 (3)	Rh2—P3—C31—C32	157.9 (4)
P3—Rh2—P7—C41	113.4 (2)	C36—C31—C32—C33	1.0 (9)
P5—Rh2—P8—C45	121.2 (2)	P3—C31—C32—C33	−168.7 (5)
P7—Rh2—P8—C45	−74.5 (2)	C31—C32—C33—C34	0.4 (10)
P3—Rh2—P8—C45	−3.1 (3)	C32—C33—C34—C35	−1.5 (11)
P5—Rh2—P8—C47	−116.8 (2)	C33—C34—C35—C36	1.0 (10)
P7—Rh2—P8—C47	47.5 (2)	C32—C31—C36—C35	−1.5 (9)
P3—Rh2—P8—C47	118.9 (3)	P3—C31—C36—C35	168.6 (5)
P5—Rh2—P8—C40	7.0 (2)	C34—C35—C36—C31	0.5 (9)
P7—Rh2—P8—C40	171.4 (2)	C31—P3—C37—C38	66.8 (4)
P3—Rh2—P8—C40	−117.2 (3)	C''—P3—C37—C38	174.8 (4)
C13—P6—C''—P3	−84.4 (4)	Rh2—P3—C37—C38	−52.1 (4)
C1—P6—C''—P3	171.8 (3)	P3—C37—C38—P7	51.9 (5)
Rh1—P6—C''—P3	54.5 (4)	C43—P7—C38—C37	103.8 (4)
C31—P3—C''—P6	−85.4 (4)	C41—P7—C38—C37	−148.9 (4)
C37—P3—C''—P6	173.6 (4)	Rh2—P7—C38—C37	−29.1 (4)
Rh2—P3—C''—P6	59.5 (4)	C'—P5—C39—C40	−171.2 (4)
C19—P4—C'—P5	−155.0 (3)	C25—P5—C39—C40	−68.5 (4)
C4—P4—C'—P5	−49.7 (4)	Rh2—P5—C39—C40	47.5 (4)
Rh1—P4—C'—P5	82.6 (3)	P5—C39—C40—P8	−41.8 (5)
C25—P5—C'—P4	69.2 (3)	C45—P8—C40—C39	−100.7 (4)
C39—P5—C'—P4	173.3 (3)	C47—P8—C40—C39	155.5 (4)
Rh2—P5—C'—P4	−62.5 (4)	Rh2—P8—C40—C39	19.9 (5)
C13—P6—C1—C2	170.3 (4)	C38—P7—C41—C42	−50.9 (6)
C''—P6—C1—C2	−81.7 (4)	C43—P7—C41—C42	55.1 (6)
Rh1—P6—C1—C2	38.1 (4)	Rh2—P7—C41—C42	−169.5 (5)
P6—C1—C2—P2	−39.8 (5)	C38—P7—C43—C44	−61.6 (5)
C9—P2—C2—C1	−97.2 (5)	C41—P7—C43—C44	−169.3 (5)
C11—P2—C2—C1	159.6 (4)	Rh2—P7—C43—C44	62.6 (5)
Rh1—P2—C2—C1	25.3 (5)	C47—P8—C45—C46	178.4 (5)
C7—P1—C3—C4	161.3 (4)	C40—P8—C45—C46	73.0 (5)
C5—P1—C3—C4	−90.8 (4)	Rh2—P8—C45—C46	−46.8 (5)
Rh1—P1—C3—C4	25.9 (4)	C45—P8—C47—C48	−173.2 (5)
P1—C3—C4—P4	−46.9 (4)	C40—P8—C47—C48	−68.1 (5)
C19—P4—C4—C3	−64.9 (4)	Rh2—P8—C47—C48	59.5 (5)