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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 RhI atoms is tetrahedrally distorted square planar and the dihedral angle between the two coordination planes is 66.28 (5)°.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010000158X/da1112sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010000158X/da1112Isup2.hkl
Contains datablock I

CCDC reference: 145523

Comment top

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 RhI 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 RhI 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.

Experimental top

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.

Refinement top

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 Uiso = 1.2Ueq 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 top

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 top
[Figure 1] 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) top
Crystal data top
[Rh2(C25H40P4)2](BF4)2Dx = 1.516 Mg m3
Mr = 1308.3Melting point: not measured K
Monoclinic, CcMo Kα radiation, λ = 0.71073 Å
a = 15.651 (3) ÅCell parameters from 25 reflections
b = 16.048 (3) Åθ = 10.7–20.8°
c = 24.022 (5) ŵ = 0.86 mm1
β = 108.18 (3)°T = 100 K
V = 5732 (2) Å3Prism, yellow
Z = 40.48 × 0.25 × 0.23 mm
F(000) = 2688
Data collection top
Enraf-Nonius CAD-4 (with Oxford Cryostream cooler)
diffractometer
7681 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.000
Graphite monochromatorθmax = 30.0°, θmin = 2.5°
ω/2θ scansh = 2022
Absorption correction: ψ-scan
(North, et al., 1968)
k = 022
Tmin = 0.640, Tmax = 0.821l = 330
8531 measured reflections3 standard reflections every 60 min
8531 independent reflections intensity decay: 1.0%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038H-atom parameters constrained
wR(F2) = 0.095w = 1/[σ2(Fo2) + (0.0505P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.05
8531 reflectionsΔρmax = 0.73 e Å3
631 parametersΔρmin = 1.03 e Å3
2 restraintsAbsolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.02 (2)
Crystal data top
[Rh2(C25H40P4)2](BF4)2V = 5732 (2) Å3
Mr = 1308.3Z = 4
Monoclinic, CcMo Kα radiation
a = 15.651 (3) ŵ = 0.86 mm1
b = 16.048 (3) ÅT = 100 K
c = 24.022 (5) Å0.48 × 0.25 × 0.23 mm
β = 108.18 (3)°
Data collection top
Enraf-Nonius CAD-4 (with Oxford Cryostream cooler)
diffractometer
7681 reflections with I > 2σ(I)
Absorption correction: ψ-scan
(North, et al., 1968)
Rint = 0.000
Tmin = 0.640, Tmax = 0.8213 standard reflections every 60 min
8531 measured reflections intensity decay: 1.0%
8531 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.038H-atom parameters constrained
wR(F2) = 0.095Δρmax = 0.73 e Å3
S = 1.04Δρmin = 1.03 e Å3
8531 reflectionsAbsolute structure: Flack (1983)
631 parametersAbsolute structure parameter: 0.02 (2)
2 restraints
Special details top

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 (Å2) top
xyzUiso*/Ueq
Rh10.54137 (2)0.34163 (2)0.433019 (16)0.01582 (8)
Rh20.49355 (2)0.21265 (2)0.631330 (16)0.01651 (8)
P10.68098 (9)0.40179 (8)0.45212 (6)0.0194 (2)
P20.53823 (10)0.27803 (9)0.34642 (6)0.0225 (3)
P30.52431 (9)0.15659 (8)0.55018 (6)0.0183 (2)
P40.53025 (8)0.42893 (8)0.50463 (5)0.0152 (2)
P50.47600 (8)0.35384 (8)0.61483 (5)0.0162 (2)
P60.42383 (8)0.25882 (8)0.42929 (5)0.0164 (2)
P70.54240 (10)0.08381 (8)0.67262 (6)0.0211 (3)
P80.42932 (10)0.24182 (8)0.70304 (6)0.0226 (3)
B10.4444 (6)0.0356 (5)0.3715 (3)0.0340 (15)
B20.5631 (6)0.2241 (4)0.1523 (3)0.0324 (15)
F10.4927 (6)0.0269 (6)0.4289 (2)0.145 (4)
F20.4046 (5)0.1123 (3)0.3620 (4)0.097 (3)
F30.5041 (3)0.0294 (3)0.3398 (2)0.0542 (11)
F40.3808 (2)0.0263 (2)0.3583 (2)0.0400 (9)
F50.5415 (3)0.3073 (2)0.1398 (2)0.0439 (10)
F60.4957 (3)0.1872 (3)0.1698 (2)0.0531 (12)
F70.5705 (3)0.1861 (3)0.10235 (18)0.0499 (11)
F80.6436 (3)0.2183 (3)0.19724 (18)0.0541 (13)
C''0.4568 (3)0.1619 (3)0.4716 (2)0.0191 (9)
H''10.48890.12900.45070.023*
H''20.40130.13230.46800.023*
C'0.4539 (3)0.4198 (3)0.5491 (2)0.0160 (8)
H'10.39630.40200.52260.019*
H'20.44510.47600.56130.019*
C10.3746 (4)0.2183 (4)0.3540 (2)0.0238 (11)
H1A0.34020.16830.35480.029*
H1B0.33400.25950.33010.029*
C20.4488 (4)0.1983 (3)0.3268 (2)0.0260 (11)
H2A0.42310.19560.28450.031*
H2B0.47460.14430.34060.031*
C30.7004 (3)0.4754 (3)0.5143 (2)0.0212 (10)
H3A0.76380.47560.53690.025*
H3B0.68390.53120.49950.025*
C40.6450 (3)0.4503 (3)0.5538 (2)0.0196 (9)
H4A0.64410.49500.58070.023*
H4B0.67020.40100.57620.023*
C50.7669 (4)0.3213 (4)0.4780 (3)0.0299 (12)
H5A0.74880.28530.50480.036*
H5B0.76760.28750.44470.036*
C60.8634 (4)0.3508 (5)0.5090 (4)0.050 (2)
H6A0.90230.30340.52070.075*
H6B0.86470.38280.54300.075*
H6C0.88370.38480.48270.075*
C70.7199 (4)0.4610 (4)0.3998 (3)0.0296 (12)
H7A0.78060.48050.41930.036*
H7B0.72220.42420.36830.036*
C80.6611 (5)0.5355 (4)0.3737 (3)0.0340 (13)
H8A0.68540.56370.34680.051*
H8B0.65940.57300.40450.051*
H8C0.60120.51670.35330.051*
C90.5102 (5)0.3491 (4)0.2831 (3)0.0333 (14)
H9A0.55710.39090.28990.040*
H9B0.51040.31760.24870.040*
C100.4205 (6)0.3930 (5)0.2701 (3)0.0466 (18)
H10A0.41170.42870.23670.070*
H10B0.41990.42570.30340.070*
H10C0.37320.35240.26190.070*
C110.6341 (4)0.2229 (4)0.3341 (3)0.0313 (13)
H11A0.61620.20290.29400.038*
H11B0.68300.26210.33880.038*
C120.6682 (5)0.1500 (4)0.3749 (3)0.0372 (14)
H12A0.71820.12470.36620.056*
H12B0.62100.10980.36970.056*
H12C0.68730.16920.41470.056*
C130.3220 (3)0.2935 (3)0.4439 (2)0.0200 (9)
C140.2779 (4)0.3631 (4)0.4124 (3)0.0271 (11)
H140.30120.38890.38560.033*
C150.2000 (4)0.3938 (4)0.4207 (3)0.0357 (14)
H150.17210.44060.40020.043*
C160.1637 (4)0.3545 (5)0.4596 (3)0.0394 (16)
H160.11100.37450.46480.047*
C170.2060 (4)0.2860 (5)0.4904 (3)0.0371 (15)
H170.18120.25930.51610.044*
C180.2856 (4)0.2564 (4)0.4837 (3)0.0282 (12)
H180.31470.21130.50590.034*
C190.4956 (3)0.5322 (3)0.4732 (2)0.0164 (9)
C200.4474 (4)0.5397 (3)0.4136 (2)0.0231 (10)
H200.43180.49210.39060.028*
C210.4229 (4)0.6174 (4)0.3886 (3)0.0288 (12)
H210.39060.62170.34900.035*
C220.4463 (4)0.6891 (4)0.4226 (3)0.0289 (12)
H220.43010.74130.40580.035*
C230.4941 (4)0.6821 (3)0.4818 (3)0.0263 (11)
H230.51030.72980.50460.032*
C240.5178 (4)0.6044 (3)0.5070 (2)0.0230 (10)
H240.54870.60030.54680.028*
C250.5707 (3)0.4105 (3)0.6660 (2)0.0173 (9)
C260.5677 (4)0.4965 (3)0.6726 (2)0.0205 (10)
H260.51590.52590.65290.025*
C270.6436 (4)0.5392 (3)0.7094 (2)0.0231 (10)
H270.64210.59670.71340.028*
C280.7194 (4)0.4955 (4)0.7390 (2)0.0285 (12)
H280.76940.52350.76300.034*
C290.7217 (4)0.4098 (4)0.7335 (2)0.0281 (12)
H290.77310.38040.75400.034*
C300.6470 (4)0.3672 (4)0.6972 (2)0.0230 (10)
H300.64860.30950.69400.028*
C310.6431 (4)0.1602 (3)0.5533 (2)0.0232 (10)
C320.6785 (4)0.1071 (4)0.5204 (3)0.0335 (13)
H320.63990.07500.49090.040*
C330.7706 (5)0.1012 (5)0.5310 (3)0.0421 (17)
H330.79340.06570.50850.051*
C340.8275 (5)0.1474 (5)0.5743 (3)0.0421 (18)
H340.88920.14200.58170.050*
C350.7958 (4)0.2023 (4)0.6078 (3)0.0355 (14)
H350.83510.23440.63690.043*
C360.7019 (4)0.2079 (4)0.5961 (3)0.0266 (11)
H360.67910.24470.61780.032*
C370.5130 (4)0.0431 (3)0.5576 (2)0.0253 (11)
H37A0.45070.02880.55190.030*
H37B0.53260.01410.52830.030*
C380.5716 (4)0.0170 (3)0.6193 (3)0.0279 (12)
H38A0.63480.02340.62300.033*
H38B0.56060.04090.62630.033*
C390.3791 (4)0.3885 (3)0.6384 (2)0.0229 (10)
H39A0.37750.44880.64000.028*
H39B0.32310.36930.61070.028*
C400.3903 (4)0.3518 (3)0.6989 (3)0.0268 (12)
H40A0.33330.35420.70690.032*
H40B0.43370.38460.72840.032*
C410.6483 (4)0.0923 (4)0.7337 (3)0.0316 (13)
H41A0.68980.12660.72110.038*
H41B0.63590.12100.76590.038*
C420.6950 (5)0.0086 (4)0.7568 (3)0.0471 (19)
H42A0.74900.01910.78850.071*
H42B0.70990.01960.72580.071*
H42C0.65530.02560.77040.071*
C430.4737 (4)0.0133 (3)0.7012 (3)0.0266 (11)
H43A0.50960.03480.71860.032*
H43B0.45680.04180.73180.032*
C440.3895 (4)0.0161 (4)0.6549 (3)0.0373 (15)
H44A0.35640.05240.67240.056*
H44B0.40570.04560.62490.056*
H44C0.35300.03110.63790.056*
C450.3254 (4)0.1841 (4)0.6937 (3)0.0309 (13)
H45A0.34030.12660.70510.037*
H45B0.29530.20720.71990.037*
C460.2594 (4)0.1856 (4)0.6305 (3)0.0367 (14)
H46A0.20670.15400.62900.055*
H46B0.28800.16170.60430.055*
H46C0.24270.24220.61920.055*
C470.4849 (5)0.2273 (4)0.7816 (3)0.0303 (12)
H47A0.44300.24280.80220.036*
H47B0.49830.16860.78880.036*
C480.5716 (5)0.2764 (4)0.8076 (3)0.0402 (16)
H48A0.59520.26510.84890.060*
H48B0.55930.33490.80170.060*
H48C0.61480.26010.78880.060*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Rh10.01687 (16)0.01697 (16)0.01341 (16)0.00120 (14)0.00442 (13)0.00025 (14)
Rh20.02153 (18)0.01374 (15)0.01414 (16)0.00037 (14)0.00540 (14)0.00016 (14)
P10.0179 (6)0.0212 (6)0.0200 (6)0.0010 (5)0.0073 (5)0.0003 (5)
P20.0271 (7)0.0246 (6)0.0168 (6)0.0011 (5)0.0084 (5)0.0024 (5)
P30.0223 (6)0.0162 (6)0.0158 (6)0.0040 (5)0.0048 (5)0.0007 (4)
P40.0150 (5)0.0161 (5)0.0138 (5)0.0011 (4)0.0034 (4)0.0002 (4)
P50.0189 (6)0.0142 (5)0.0158 (6)0.0008 (4)0.0059 (5)0.0002 (4)
P60.0162 (6)0.0173 (5)0.0136 (5)0.0007 (4)0.0016 (5)0.0006 (4)
P70.0285 (7)0.0151 (5)0.0167 (6)0.0001 (5)0.0027 (5)0.0017 (5)
P80.0325 (7)0.0180 (6)0.0205 (6)0.0029 (5)0.0130 (6)0.0002 (5)
B10.049 (4)0.032 (3)0.021 (3)0.008 (3)0.013 (3)0.003 (3)
B20.044 (4)0.024 (3)0.023 (3)0.001 (3)0.002 (3)0.001 (2)
F10.191 (8)0.180 (8)0.024 (3)0.150 (7)0.023 (4)0.024 (3)
F20.143 (6)0.027 (2)0.173 (7)0.004 (3)0.124 (6)0.012 (3)
F30.045 (2)0.058 (3)0.062 (3)0.004 (2)0.020 (2)0.006 (2)
F40.0273 (18)0.0305 (19)0.056 (3)0.0017 (15)0.0038 (18)0.0073 (18)
F50.059 (3)0.0238 (17)0.052 (3)0.0063 (17)0.022 (2)0.0048 (17)
F60.044 (2)0.046 (2)0.065 (3)0.015 (2)0.011 (2)0.009 (2)
F70.077 (3)0.034 (2)0.033 (2)0.005 (2)0.009 (2)0.0079 (18)
F80.038 (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)
C10.023 (3)0.028 (3)0.014 (2)0.003 (2)0.004 (2)0.0025 (19)
C20.033 (3)0.025 (3)0.021 (3)0.006 (2)0.009 (2)0.009 (2)
C30.015 (2)0.023 (2)0.025 (3)0.0029 (18)0.005 (2)0.005 (2)
C40.016 (2)0.024 (2)0.019 (2)0.0033 (18)0.0053 (18)0.0010 (19)
C50.026 (3)0.030 (3)0.031 (3)0.009 (2)0.005 (2)0.004 (2)
C60.026 (3)0.051 (4)0.058 (5)0.016 (3)0.010 (3)0.026 (4)
C70.033 (3)0.031 (3)0.030 (3)0.002 (2)0.017 (3)0.000 (2)
C80.040 (3)0.030 (3)0.035 (3)0.003 (3)0.016 (3)0.011 (3)
C90.045 (4)0.036 (3)0.019 (3)0.007 (3)0.012 (3)0.000 (2)
C100.063 (5)0.047 (4)0.028 (3)0.013 (4)0.012 (3)0.008 (3)
C110.037 (3)0.034 (3)0.028 (3)0.003 (2)0.018 (3)0.009 (2)
C120.038 (3)0.036 (3)0.037 (3)0.001 (3)0.009 (3)0.011 (3)
C130.018 (2)0.023 (2)0.016 (2)0.0014 (18)0.0016 (18)0.0010 (18)
C140.021 (2)0.028 (3)0.029 (3)0.003 (2)0.003 (2)0.001 (2)
C150.023 (3)0.040 (3)0.041 (4)0.010 (2)0.005 (3)0.000 (3)
C160.019 (3)0.048 (4)0.051 (4)0.010 (3)0.010 (3)0.007 (3)
C170.022 (3)0.054 (4)0.035 (4)0.003 (3)0.009 (3)0.008 (3)
C180.022 (3)0.030 (3)0.030 (3)0.004 (2)0.004 (2)0.005 (2)
C190.016 (2)0.0133 (19)0.021 (2)0.0022 (16)0.0067 (18)0.0005 (17)
C200.027 (3)0.023 (2)0.019 (2)0.005 (2)0.007 (2)0.003 (2)
C210.035 (3)0.029 (3)0.023 (3)0.008 (2)0.009 (2)0.006 (2)
C220.036 (3)0.022 (3)0.032 (3)0.006 (2)0.016 (3)0.008 (2)
C230.031 (3)0.018 (2)0.034 (3)0.002 (2)0.016 (3)0.003 (2)
C240.023 (2)0.023 (2)0.024 (3)0.003 (2)0.009 (2)0.004 (2)
C250.020 (2)0.020 (2)0.011 (2)0.0003 (18)0.0028 (17)0.0026 (17)
C260.028 (3)0.018 (2)0.016 (2)0.0022 (19)0.007 (2)0.0004 (18)
C270.032 (3)0.020 (2)0.016 (2)0.003 (2)0.007 (2)0.0002 (19)
C280.029 (3)0.034 (3)0.019 (2)0.009 (2)0.003 (2)0.001 (2)
C290.030 (3)0.038 (3)0.015 (2)0.002 (2)0.004 (2)0.005 (2)
C300.027 (3)0.024 (2)0.016 (2)0.006 (2)0.005 (2)0.0047 (19)
C310.022 (2)0.029 (3)0.017 (2)0.011 (2)0.0038 (19)0.004 (2)
C320.036 (3)0.037 (3)0.027 (3)0.018 (3)0.009 (3)0.000 (2)
C330.038 (4)0.048 (4)0.043 (4)0.025 (3)0.016 (3)0.008 (3)
C340.030 (3)0.054 (4)0.043 (4)0.020 (3)0.014 (3)0.017 (3)
C350.021 (3)0.049 (4)0.032 (3)0.001 (3)0.002 (2)0.006 (3)
C360.024 (3)0.034 (3)0.023 (3)0.004 (2)0.009 (2)0.008 (2)
C370.038 (3)0.015 (2)0.020 (2)0.006 (2)0.005 (2)0.0013 (19)
C380.044 (3)0.018 (2)0.022 (3)0.005 (2)0.010 (2)0.004 (2)
C390.023 (2)0.022 (2)0.028 (3)0.0049 (19)0.013 (2)0.003 (2)
C400.041 (3)0.022 (2)0.025 (3)0.000 (2)0.021 (2)0.001 (2)
C410.038 (3)0.024 (3)0.026 (3)0.001 (2)0.001 (2)0.001 (2)
C420.053 (4)0.032 (3)0.034 (3)0.003 (3)0.019 (3)0.008 (3)
C430.036 (3)0.018 (2)0.024 (3)0.007 (2)0.008 (2)0.001 (2)
C440.037 (3)0.029 (3)0.046 (4)0.008 (3)0.012 (3)0.005 (3)
C450.032 (3)0.033 (3)0.033 (3)0.008 (2)0.019 (3)0.003 (2)
C460.034 (3)0.037 (3)0.042 (4)0.013 (3)0.017 (3)0.001 (3)
C470.047 (4)0.023 (3)0.023 (3)0.004 (2)0.013 (3)0.003 (2)
C480.065 (5)0.030 (3)0.020 (3)0.001 (3)0.007 (3)0.000 (2)
Geometric parameters (Å, º) top
Rh1—P62.2483 (14)B2—F61.385 (9)
Rh1—P42.2670 (13)B2—F51.387 (8)
Rh1—P12.3003 (15)C1—C21.534 (8)
Rh1—P22.3039 (15)C3—C41.525 (7)
Rh2—P82.2973 (15)C5—C61.536 (9)
Rh2—P52.3018 (13)C7—C81.519 (8)
Rh2—P72.3174 (14)C9—C101.513 (10)
Rh2—P32.3295 (14)C11—C121.512 (9)
P1—C71.825 (6)C13—C181.390 (8)
P1—C51.829 (6)C13—C141.403 (7)
P1—C31.854 (5)C14—C151.385 (8)
P2—C91.842 (6)C15—C161.388 (10)
P2—C111.844 (6)C16—C171.374 (10)
P2—C21.845 (6)C17—C181.388 (9)
P3—C311.838 (6)C19—C241.395 (7)
P3—C371.844 (5)C19—C201.399 (7)
P3—C''1.856 (5)C20—C211.386 (8)
P4—C191.832 (5)C21—C221.392 (9)
P4—C'1.840 (5)C22—C231.389 (9)
P4—C41.847 (5)C23—C241.385 (8)
P5—C'1.843 (5)C25—C301.383 (7)
P5—C251.844 (5)C25—C261.391 (7)
P5—C391.862 (5)C26—C271.417 (8)
P6—C131.823 (5)C27—C281.370 (8)
P6—C''1.840 (5)C28—C291.383 (9)
P6—C11.850 (5)C29—C301.400 (8)
P7—C381.833 (6)C31—C361.380 (8)
P7—C431.835 (6)C31—C321.389 (8)
P7—C411.844 (6)C32—C331.386 (9)
P8—C451.824 (6)C33—C341.359 (11)
P8—C471.830 (6)C34—C351.384 (10)
P8—C401.860 (6)C35—C361.410 (8)
B1—F11.356 (9)C37—C381.538 (8)
B1—F21.366 (9)C39—C401.526 (8)
B1—F41.371 (8)C41—C421.547 (9)
B1—F31.380 (9)C43—C441.510 (9)
B2—F71.382 (8)C45—C461.545 (10)
B2—F81.383 (9)C47—C481.523 (9)
P6—Rh1—P498.05 (5)F1—B1—F4107.1 (6)
P6—Rh1—P1166.04 (5)F2—B1—F4110.7 (7)
P4—Rh1—P183.24 (5)F1—B1—F3107.2 (8)
P6—Rh1—P285.16 (6)F2—B1—F3109.0 (6)
P4—Rh1—P2166.88 (5)F4—B1—F3112.8 (6)
P1—Rh1—P296.74 (6)F7—B2—F8110.2 (6)
P8—Rh2—P582.64 (5)F7—B2—F6110.7 (6)
P8—Rh2—P791.37 (5)F8—B2—F6109.1 (6)
P5—Rh2—P7163.27 (5)F7—B2—F5108.5 (5)
P8—Rh2—P3163.57 (5)F8—B2—F5109.6 (6)
P5—Rh2—P3106.31 (5)F6—B2—F5108.7 (6)
P7—Rh2—P383.50 (5)P6—C''—P3125.0 (3)
C7—P1—C5103.6 (3)P4—C'—P5124.1 (3)
C7—P1—C3102.6 (3)C2—C1—P6110.4 (4)
C5—P1—C3104.9 (3)C1—C2—P2111.2 (4)
C7—P1—Rh1125.6 (2)C4—C3—P1110.5 (3)
C5—P1—Rh1108.9 (2)C3—C4—P4106.3 (3)
C3—P1—Rh1109.57 (17)C6—C5—P1117.0 (5)
C9—P2—C1199.3 (3)C8—C7—P1113.9 (4)
C9—P2—C2104.6 (3)C10—C9—P2115.2 (5)
C11—P2—C2102.5 (3)C12—C11—P2114.1 (4)
C9—P2—Rh1113.8 (2)C18—C13—C14118.2 (5)
C11—P2—Rh1124.6 (2)C18—C13—P6124.9 (4)
C2—P2—Rh1109.77 (18)C14—C13—P6116.9 (4)
C31—P3—C3798.8 (3)C15—C14—C13120.9 (6)
C31—P3—C''106.7 (2)C14—C15—C16119.9 (6)
C37—P3—C''95.9 (2)C17—C16—C15119.8 (6)
C31—P3—Rh2115.13 (19)C16—C17—C18120.6 (6)
C37—P3—Rh2104.47 (19)C17—C18—C13120.6 (6)
C''—P3—Rh2129.24 (17)C24—C19—C20118.8 (5)
C19—P4—C'98.6 (2)C24—C19—P4121.6 (4)
C19—P4—C4101.5 (2)C20—C19—P4119.7 (4)
C'—P4—C4108.8 (2)C21—C20—C19120.5 (5)
C19—P4—Rh1109.22 (17)C20—C21—C22120.2 (5)
C'—P4—Rh1127.50 (16)C23—C22—C21119.5 (5)
C4—P4—Rh1108.06 (17)C24—C23—C22120.4 (5)
C'—P5—C25100.6 (2)C23—C24—C19120.6 (5)
C'—P5—C3997.8 (2)C30—C25—C26119.5 (5)
C25—P5—C39102.2 (2)C30—C25—P5119.4 (4)
C'—P5—Rh2133.93 (16)C26—C25—P5121.1 (4)
C25—P5—Rh2110.07 (16)C25—C26—C27119.9 (5)
C39—P5—Rh2107.83 (18)C28—C27—C26119.9 (5)
C13—P6—C''105.3 (2)C27—C28—C29120.2 (5)
C13—P6—C1100.0 (2)C28—C29—C30120.3 (5)
C''—P6—C1101.7 (2)C25—C30—C29120.2 (5)
C13—P6—Rh1124.43 (18)C36—C31—C32118.2 (5)
C''—P6—Rh1113.12 (17)C36—C31—P3118.6 (4)
C1—P6—Rh1109.44 (19)C32—C31—P3122.4 (5)
C38—P7—C43101.8 (3)C33—C32—C31120.9 (6)
C38—P7—C41103.9 (3)C34—C33—C32119.9 (6)
C43—P7—C41103.5 (3)C33—C34—C35121.6 (6)
C38—P7—Rh2110.09 (18)C34—C35—C36117.7 (6)
C43—P7—Rh2123.8 (2)C31—C36—C35121.6 (6)
C41—P7—Rh2111.7 (2)C38—C37—P3108.4 (4)
C45—P8—C47100.5 (3)C37—C38—P7108.1 (4)
C45—P8—C40102.1 (3)C40—C39—P5108.2 (4)
C47—P8—C40102.6 (3)C39—C40—P8110.8 (4)
C45—P8—Rh2112.7 (2)C42—C41—P7115.4 (4)
C47—P8—Rh2124.7 (2)C44—C43—P7113.3 (4)
C40—P8—Rh2111.49 (17)C46—C45—P8114.2 (4)
F1—B1—F2110.0 (8)C48—C47—P8115.7 (4)
P6—Rh1—P1—C7145.0 (3)C'—P4—C4—C3168.2 (3)
P4—Rh1—P1—C7118.9 (2)Rh1—P4—C4—C349.9 (4)
P2—Rh1—P1—C747.9 (2)C7—P1—C5—C660.8 (6)
P6—Rh1—P1—C521.7 (3)C3—P1—C5—C646.4 (6)
P4—Rh1—P1—C5117.8 (2)Rh1—P1—C5—C6163.6 (5)
P2—Rh1—P1—C575.4 (2)C5—P1—C7—C8177.3 (5)
P6—Rh1—P1—C392.5 (3)C3—P1—C7—C868.3 (5)
P4—Rh1—P1—C33.64 (19)Rh1—P1—C7—C857.2 (5)
P2—Rh1—P1—C3170.42 (19)C11—P2—C9—C10167.1 (5)
P6—Rh1—P2—C9115.1 (2)C2—P2—C9—C1061.5 (6)
P4—Rh1—P2—C910.3 (4)Rh1—P2—C9—C1058.3 (6)
P1—Rh1—P2—C978.8 (2)C9—P2—C11—C12172.6 (5)
P6—Rh1—P2—C11123.7 (3)C2—P2—C11—C1265.3 (5)
P4—Rh1—P2—C11131.5 (3)Rh1—P2—C11—C1259.8 (5)
P1—Rh1—P2—C1142.4 (3)C''—P6—C13—C185.7 (5)
P6—Rh1—P2—C21.8 (2)C1—P6—C13—C18110.9 (5)
P4—Rh1—P2—C2106.6 (3)Rh1—P6—C13—C18127.1 (4)
P1—Rh1—P2—C2164.3 (2)C''—P6—C13—C14174.4 (4)
P8—Rh2—P3—C31153.8 (2)C1—P6—C13—C1469.3 (5)
P5—Rh2—P3—C3184.8 (2)Rh1—P6—C13—C1452.7 (5)
P7—Rh2—P3—C3181.3 (2)C18—C13—C14—C150.2 (9)
P8—Rh2—P3—C3746.6 (3)P6—C13—C14—C15180.0 (5)
P5—Rh2—P3—C37168.0 (2)C13—C14—C15—C161.4 (10)
P7—Rh2—P3—C3725.9 (2)C14—C15—C16—C170.9 (11)
P8—Rh2—P3—C''63.7 (3)C15—C16—C17—C181.0 (11)
P5—Rh2—P3—C''57.6 (2)C16—C17—C18—C132.5 (10)
P7—Rh2—P3—C''136.2 (2)C14—C13—C18—C172.1 (9)
P6—Rh1—P4—C19111.27 (17)P6—C13—C18—C17178.1 (5)
P1—Rh1—P4—C1982.75 (17)C'—P4—C19—C2471.9 (4)
P2—Rh1—P4—C197.9 (3)C4—P4—C19—C2439.4 (5)
P6—Rh1—P4—C'6.5 (2)Rh1—P4—C19—C24153.3 (4)
P1—Rh1—P4—C'159.5 (2)C'—P4—C19—C20109.5 (4)
P2—Rh1—P4—C'109.9 (3)C4—P4—C19—C20139.3 (4)
P6—Rh1—P4—C4139.12 (18)Rh1—P4—C19—C2025.3 (4)
P1—Rh1—P4—C426.86 (18)C24—C19—C20—C210.5 (8)
P2—Rh1—P4—C4117.5 (3)P4—C19—C20—C21178.1 (4)
P8—Rh2—P5—C'148.0 (2)C19—C20—C21—C220.3 (9)
P7—Rh2—P5—C'142.3 (3)C20—C21—C22—C230.3 (9)
P3—Rh2—P5—C'17.9 (2)C21—C22—C23—C240.5 (9)
P8—Rh2—P5—C2583.37 (17)C22—C23—C24—C191.3 (8)
P7—Rh2—P5—C2513.6 (3)C20—C19—C24—C231.3 (7)
P3—Rh2—P5—C25110.72 (17)P4—C19—C24—C23177.3 (4)
P8—Rh2—P5—C3927.4 (2)C'—P5—C25—C30131.1 (4)
P7—Rh2—P5—C3997.2 (3)C39—P5—C25—C30128.4 (4)
P3—Rh2—P5—C39138.5 (2)Rh2—P5—C25—C3014.0 (4)
P4—Rh1—P6—C1332.0 (2)C'—P5—C25—C2647.2 (4)
P1—Rh1—P6—C13126.3 (3)C39—P5—C25—C2653.3 (5)
P2—Rh1—P6—C13135.2 (2)Rh2—P5—C25—C26167.7 (4)
P4—Rh1—P6—C''97.76 (18)C30—C25—C26—C272.3 (8)
P1—Rh1—P6—C''3.4 (3)P5—C25—C26—C27176.0 (4)
P2—Rh1—P6—C''95.05 (18)C25—C26—C27—C280.9 (8)
P4—Rh1—P6—C1149.6 (2)C26—C27—C28—C290.5 (8)
P1—Rh1—P6—C1116.0 (3)C27—C28—C29—C300.6 (9)
P2—Rh1—P6—C117.5 (2)C26—C25—C30—C292.3 (8)
P8—Rh2—P7—C38162.9 (2)P5—C25—C30—C29176.1 (4)
P5—Rh2—P7—C38128.6 (3)C28—C29—C30—C250.8 (8)
P3—Rh2—P7—C381.5 (2)C37—P3—C31—C36122.4 (5)
P8—Rh2—P7—C4342.5 (2)C''—P3—C31—C36138.7 (4)
P5—Rh2—P7—C43111.0 (3)Rh2—P3—C31—C3611.8 (5)
P3—Rh2—P7—C43121.9 (2)C37—P3—C31—C3247.3 (5)
P8—Rh2—P7—C4182.2 (2)C''—P3—C31—C3251.6 (5)
P5—Rh2—P7—C4113.7 (3)Rh2—P3—C31—C32157.9 (4)
P3—Rh2—P7—C41113.4 (2)C36—C31—C32—C331.0 (9)
P5—Rh2—P8—C45121.2 (2)P3—C31—C32—C33168.7 (5)
P7—Rh2—P8—C4574.5 (2)C31—C32—C33—C340.4 (10)
P3—Rh2—P8—C453.1 (3)C32—C33—C34—C351.5 (11)
P5—Rh2—P8—C47116.8 (2)C33—C34—C35—C361.0 (10)
P7—Rh2—P8—C4747.5 (2)C32—C31—C36—C351.5 (9)
P3—Rh2—P8—C47118.9 (3)P3—C31—C36—C35168.6 (5)
P5—Rh2—P8—C407.0 (2)C34—C35—C36—C310.5 (9)
P7—Rh2—P8—C40171.4 (2)C31—P3—C37—C3866.8 (4)
P3—Rh2—P8—C40117.2 (3)C''—P3—C37—C38174.8 (4)
C13—P6—C''—P384.4 (4)Rh2—P3—C37—C3852.1 (4)
C1—P6—C''—P3171.8 (3)P3—C37—C38—P751.9 (5)
Rh1—P6—C''—P354.5 (4)C43—P7—C38—C37103.8 (4)
C31—P3—C''—P685.4 (4)C41—P7—C38—C37148.9 (4)
C37—P3—C''—P6173.6 (4)Rh2—P7—C38—C3729.1 (4)
Rh2—P3—C''—P659.5 (4)C'—P5—C39—C40171.2 (4)
C19—P4—C'—P5155.0 (3)C25—P5—C39—C4068.5 (4)
C4—P4—C'—P549.7 (4)Rh2—P5—C39—C4047.5 (4)
Rh1—P4—C'—P582.6 (3)P5—C39—C40—P841.8 (5)
C25—P5—C'—P469.2 (3)C45—P8—C40—C39100.7 (4)
C39—P5—C'—P4173.3 (3)C47—P8—C40—C39155.5 (4)
Rh2—P5—C'—P462.5 (4)Rh2—P8—C40—C3919.9 (5)
C13—P6—C1—C2170.3 (4)C38—P7—C41—C4250.9 (6)
C''—P6—C1—C281.7 (4)C43—P7—C41—C4255.1 (6)
Rh1—P6—C1—C238.1 (4)Rh2—P7—C41—C42169.5 (5)
P6—C1—C2—P239.8 (5)C38—P7—C43—C4461.6 (5)
C9—P2—C2—C197.2 (5)C41—P7—C43—C44169.3 (5)
C11—P2—C2—C1159.6 (4)Rh2—P7—C43—C4462.6 (5)
Rh1—P2—C2—C125.3 (5)C47—P8—C45—C46178.4 (5)
C7—P1—C3—C4161.3 (4)C40—P8—C45—C4673.0 (5)
C5—P1—C3—C490.8 (4)Rh2—P8—C45—C4646.8 (5)
Rh1—P1—C3—C425.9 (4)C45—P8—C47—C48173.2 (5)
P1—C3—C4—P446.9 (4)C40—P8—C47—C4868.1 (5)
C19—P4—C4—C364.9 (4)Rh2—P8—C47—C4859.5 (5)

Experimental details

Crystal data
Chemical formula[Rh2(C25H40P4)2](BF4)2
Mr1308.3
Crystal system, space groupMonoclinic, Cc
Temperature (K)100
a, b, c (Å)15.651 (3), 16.048 (3), 24.022 (5)
β (°) 108.18 (3)
V3)5732 (2)
Z4
Radiation typeMo Kα
µ (mm1)0.86
Crystal size (mm)0.48 × 0.25 × 0.23
Data collection
DiffractometerEnraf-Nonius CAD-4 (with Oxford Cryostream cooler)
diffractometer
Absorption correctionψ-scan
(North, et al., 1968)
Tmin, Tmax0.640, 0.821
No. of measured, independent and
observed [I > 2σ(I)] reflections
8531, 8531, 7681
Rint0.000
(sin θ/λ)max1)0.703
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.095, 1.04
No. of reflections8531
No. of parameters631
No. of restraints2
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.73, 1.03
Absolute structureFlack (1983)
Absolute structure parameter0.02 (2)

Computer programs: CAD-4 EXPRESS (Enraf-Nonius, 1994), XCAD4 (Harms & Wocadlo, 1996), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996; Farrugia, 1997), SHELXTL (Bruker, 1998).

Selected geometric parameters (Å, º) top
Rh1—P62.2483 (14)Rh2—P72.3174 (14)
Rh1—P42.2670 (13)Rh2—P32.3295 (14)
Rh1—P12.3003 (15)P3—C''1.856 (5)
Rh1—P22.3039 (15)P4—C'1.840 (5)
Rh2—P82.2973 (15)P5—C'1.843 (5)
Rh2—P52.3018 (13)P6—C''1.840 (5)
P6—Rh1—P498.05 (5)P8—Rh2—P791.37 (5)
P6—Rh1—P1166.04 (5)P5—Rh2—P7163.27 (5)
P4—Rh1—P183.24 (5)P8—Rh2—P3163.57 (5)
P6—Rh1—P285.16 (6)P5—Rh2—P3106.31 (5)
P4—Rh1—P2166.88 (5)P7—Rh2—P383.50 (5)
P1—Rh1—P296.74 (6)P6—C''—P3125.0 (3)
P8—Rh2—P582.64 (5)P4—C'—P5124.1 (3)
 

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