An arene–ruthenium(II) complex containing novel hybrid phosphinofluoro ligands

In the title compound, (η⁶-p-cymene)[(di­phenyl­phos­phino­fluorido)­tri­fluoro­borato-κ²P,F][(di­phenyl­phos­phin­oyl­fluorido)­tri­fluoro­borato-κO]ruthenium(II), [Ru(C₁₂H₁₀BF₄OP)(C₁₂H₁₀BF₄P)(C₁₀H₁₄)], the hybrid Ph₂PFBF₃ ligand is bidentate (κ²P,F) and thus forms a five-membered chelate ring. The Ph₂PFBF₃ ligand is unusually ligated to the metal through the P atom of the PPh₂ moiety and through one of the F atoms of the BF₄ moiety. The phosphine-oxidized Ph₂P(O)FBF₃ ligand is bonded to the Ru atom via the O atom. The Ru centre has a pseudo-octahedral coordination environment, in which the phenyl ring occupies three of the corners of the distorted octahedron. The Ru—O, Ru—F and Ru—P bond lengths are 2.107 (3), 2.135 (4) and 2.3145 (15) Å, respectively.

S1. Comment

The chemistry of half-sandwich (η⁶-arene)ruthenium(II) complexes is currently of much interest because of the numerous applications in new catalytic systems for a variety of organic transformation reactions (Noyori, 1994). Ruthenium-based catalytic systems are found to be effective in the hydrogenation of ketones for the synthesis of chiral alcohols (Bernard et al., 2000). Studies by Noyori and coworkers have shown that the transfer hydrogenation of prochiral ketones can be achieved by high enantiomeric excess by tailoring the chiral ruthenium catalysts; accordingly, investigations of chiral ruthenium catalysts are now common (Yamakawa et al., 2000). In the course of our research on ruthenium complexes with S and Se donor ligands, we are interested in preparing some new bulk ligands by the hybridization of different atoms (Zhang et al., 2002). The most intriguing properties of alkylphosphine ligands are related to the strong σ-donor P atom and electron-donating alkyl groups, which can stabilize the 16 e ruthenium species ?so that they? convert to their 18 e congeners by oxidative addition at the metal centre (Halpern, 1970). Tetrafluoroborate as a ligand in the reactive complexes can be easily replaced by π and σ donors, suggesting that it is a very good leaving group (Appel & Beck, 1985). Thus, we attempted the reaction of Ph₂PCl and Ag[BF₄] in order to isolate the hybrid phosphine-fluoro ligand Ph₂PFBF₃ with one P—F bond (Scheme 1). In order to reveal coordination modes of this ligand in the ruthenium complexes, we prepared the title complex, (I), and carried out a diffraction analysis. In this paper, we report our initial findings on the structure of [(η⁶-p-cymene)Ru(η²-Ph₂PFBF₃—P,F)(η¹-Ph₂P(O)FBF₃—O)]. To our knowledge, this is the first structural example of a transition metal complex containing the hybrid ligand Ph₂PFBF₃.

In the neutral complex, (I), the Ru atom exhibits a distorted octahedral coordination sphere, with the phenyl ring of p-cymene ligand formally occupying three octahedral sites. The structure of (I) is depicted in Fig. 1. The O atom of Ph₂P(O)FBF₃ and the Ph₂PFBF₃ chelate bidentate ligand, bonded to the metal center through the P? and F atoms complete the coordination sphere, which may infer that the Ru atom exhibits a chiral centre. The hybrid Ph₂PFBF₃ ligand is unusually η²-ligated to the metal by the P atom in the PPh₂ moiety and one of the F atoms in the BF₄ moiety. This novel coordination mode is the first example of a ruthenium complex system. Ph₂PFBF₃ acts as a bidentate ligand to form a five-membered chelate ring with a bite angle of 78.48 (12)°, which is obviously more acute than that found for the Me₂PCHCHPMe₂ bidentate phosphino ligand in Ru(II) complexes (Field et al., 1994). The Ru—C(ring) distances span the range 2.158 (5)–2.245 (7) Å and agree well with those found in other p-(cymene)ruthenium(II) complexes, [(p-cymene)RuCl(Me₂PCH₂CH₂SMe)][BPh₄] [2.198 (5)–2.267 (6) Å; Suzuki et al., 1996] and [(p-cymene)RuCl₂(PH₂Cy) [2.175 (4)—2.238 (5) Å; Van der Maelen Uría et al., 1994]. Note that the longest Ru—C bond [Ru(1)—C(6) = 2.245 (7) Å] is trans with respect to the P atom, which results from the strong trans influence of the PPh₂ group. The Ru—O bond length of 2.107 (3) Å in (I) indicates considerable single- bond character. The Ru—F bond length of 2.135 (4) Å in (I) is significantly ? compared with those in cis-[Ru(dmpe)₂F(F···HF)] [2.101 (3) and 2.168 (3) Å] (Kirkham et al., 2001). The Ru—P bond distance of 2.3147 (15) Å is normal, and also agrees excellently with those in other related complexes (Suzuki et al., 1996; Van der Maelen Uría et al., 1994).

The P2—F5 bond length of the coordinated chelate ligand [1.582 (4) Å] is slightly longer than the P1—F1 bond length of the terminal coordination ligand [1.552 (4) Å]. There are three types of B—F bonds in (I), viz. the B-µ-F(P) bond [B2—F5 = 1.485 (8) Å and B1—F1 = 1.472 (8) Å], the B-µ-F(Ru) bond [B2—F6 = 1.452 (8) Å] and the terminal B—F bond [1.344 (9)—1.399 (8) Å]. On the other hand, the B2—F5—P2 angle [120.2 (4)°] is smaller than the B1—F1—P1 angle [134.8 (4)°] and that in the reported complex [Mo(η⁵-C₉H₇)(CO)₂{P-η³-{^tBu}CPC(^tBu)PFBF₃}] [131.1 (6)°; Hitchcock et al., 1994]. Thus, it is reasonable ?to say? that the coordination of the Ph₂PFBF₃ chleate ligand to the Ru atom results in the elongation of the P—F and B-µ-F(P) bonds and the reduction of the B—F—P angle (Barthazy et al., 2000). Angles involving the P atoms reflect a tetrahedral geometry, and it is also noteworthy that the Ru—P—C and O—P—F angles are larger than the F—P—C angles.

S2. Experimental

Preparations of ligands (see Reaction Scheme): Treatment of Ph₂PCl in dry CH₂Cl₂ with an equal equivalent of Ag[BF₄] resulted in a light yellow solution with a white precipitate. The solution was filtered to remove the AgCl precipitate and the solvent was pumped off to give a yellow oily product, viz. Ph₂PFBF₃. Spectroscopic analysis; ¹H NMR (CDCl₃, p.p.m.): δ −7.12—7.75 (m, Ph); ³¹P{¹H} NMR (CDCl₃, p.p.m.): δ −76.5; ¹⁹F NMR (CDCl₃, p.p.m.): δ −187.2 (d, J = 118 Hz, PFB), −319.3 (BF₃); MS (EI): m/z 273 (M⁺ + 1); IR (Nujol, cm⁻¹): ν (B—F) 1154(s), 901(s), 856(s) and 712(m). The oily Ph₂PFBF₃ was dissolved in CH₂Cl₂, affording the oxo-phosphino compound Ph₂P(O)FBF₃. Spectrocopic analysis; ¹H NMR (CDCl₃, p.p.m.): δ 7.09—7.77 (m, Ph); ³¹P{¹H} NMR (CDCl₃, p.p.m.): δ 84.1; ¹⁹F NMR (CDCl₃, p.p.m.): δ −164.6 (d, J = 96 Hz, PFB), −302.7 (BF₃); MS (EI): m/z 288 (M⁺); IR (Nujol, cm⁻¹): ν(B—F) 1148(s), 892(s), 843(s) and 716(m); ν(P=O) 1016(versus).

Synthesis of (I): Ph₂PFBF₃ (272 mg, 1.0 mmol) was dissolved in CH₂Cl₂ (5 ml) and the solution was added to a flask containing a solution of [(p-cymene)Ru(acetone)₃][BF₄] (248 mg, 0.5 mmol) in CH₂Cl₂ (5 ml). The solution was stirred for 2 h and the solvent was removed in vacuo to 5 ml. Hexane (20 ml) was added to the flask to give an orange precipitate. Recrystallization from CH₂Cl₂/hexane afforded orange prismatic crystals.

S3. Refinement

H atoms were treated as riding atoms using the normal SHELXTL parameters.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT-Plus (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. A perspective view of (I). H atoms have been omitted for clarity and displacement ellipsoids are drawn at the 50% probability level.

(η⁶-p-cymene)[(η²-diphenylphosphino-tetrafluroborate-P,F) (η¹-diphenylphosphinoyl-tetrafluroborate-O)]ruthenium(II)

Crystal data

C34H34B2F8OP2Ru	F(000) = 1608
Mr = 795.24	Dx = 1.550 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 3433 reflections
a = 17.7179 (13) Å	θ = 2.2–25.6°
b = 11.2784 (8) Å	µ = 0.63 mm^−1
c = 18.4455 (13) Å	T = 294 K
β = 112.410 (2)°	Prism, orange
V = 3407.6 (4) Å^3	0.22 × 0.18 × 0.15 mm
Z = 4

Data collection

Bruker SMART APEX CCD diffractometer	6382 independent reflections
Radiation source: fine-focus sealed tube	5757 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
ω scans	θmax = 26.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS, Sheldrick, 1996)	h = −21→21
Tmin = 0.294, Tmax = 0.401	k = −11→13
10808 measured reflections	l = −22→22

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)] = 0.043	H-atom parameters constrained
wR(F^2) = 0.098	w = 1/[σ^2(Fo^2) + (0.0476P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max < 0.001
6382 reflections	Δρmax = 1.07 e Å^−3
439 parameters	Δρmin = −0.28 e Å^−3
0 restraints	Absolute structure: (Flack, 1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.03 (3)

Special details

Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 20 s covered 0.3° in ω. The crystal-to-detector distance was 4 cm and the detector swing angle was −35°. Coverage of the unique set is over 99% complete.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Ru1	1.008029 (14)	0.91034 (3)	0.753220 (14)	0.03492 (10)
P1	1.03990 (9)	1.21096 (12)	0.74676 (8)	0.0453 (3)
P2	0.90917 (9)	0.89087 (13)	0.62816 (9)	0.0363 (3)
O1	1.0010 (3)	1.0930 (3)	0.7276 (2)	0.0544 (10)
F1	1.1286 (2)	1.2119 (4)	0.8090 (2)	0.0808 (11)
F2	1.1932 (2)	1.0854 (3)	0.7499 (2)	0.0778 (11)
F3	1.2367 (3)	1.0962 (4)	0.8809 (3)	0.0987 (17)
F4	1.2568 (3)	1.2490 (4)	0.8124 (3)	0.1009 (14)
F5	0.9556 (2)	0.8941 (3)	0.5700 (2)	0.0667 (9)
F6	1.0804 (2)	0.9114 (3)	0.6835 (3)	0.0681 (12)
F7	1.0638 (3)	0.7633 (4)	0.5913 (3)	0.0968 (14)
F8	1.0751 (3)	0.9530 (5)	0.5575 (2)	0.0968 (15)
B1	1.2064 (4)	1.1590 (7)	0.8140 (4)	0.0581 (17)
B2	1.0458 (4)	0.8819 (7)	0.6006 (4)	0.0567 (17)
C1	0.9074 (5)	0.9995 (7)	0.8661 (4)	0.083 (2)
H1A	0.9158	0.9962	0.9206	0.124*
H1B	0.8526	0.9753	0.8349	0.124*
H1C	0.9158	1.0792	0.8525	0.124*
C2	0.9665 (4)	0.9181 (6)	0.8507 (4)	0.061 (2)
C3	0.9393 (4)	0.8108 (5)	0.8073 (3)	0.0550 (14)
H3	0.8841	0.7914	0.7879	0.066*
C4	0.9947 (4)	0.7350 (5)	0.7937 (3)	0.0527 (14)
H4	0.9759	0.6656	0.7653	0.063*
C5	1.0784 (4)	0.7615 (5)	0.8221 (3)	0.0505 (13)
C6	1.1059 (4)	0.8638 (6)	0.8694 (4)	0.0527 (16)
H6	1.1615	0.8798	0.8922	0.063*
C7	1.0520 (4)	0.9390 (5)	0.8818 (3)	0.0570 (15)
H7	1.0719	1.0066	0.9118	0.068*
C8	1.1357 (4)	0.6794 (6)	0.8043 (4)	0.0732 (19)
H8	1.1116	0.6581	0.7486	0.088*
C9	1.1451 (7)	0.5656 (7)	0.8535 (7)	0.130 (4)
H9A	1.1851	0.5785	0.9054	0.196*
H9B	1.1625	0.5015	0.8292	0.196*
H9C	1.0937	0.5460	0.8565	0.196*
C10	1.2201 (6)	0.7326 (9)	0.8217 (7)	0.122 (4)
H10A	1.2146	0.8049	0.7927	0.184*
H10B	1.2527	0.6774	0.8066	0.184*
H10C	1.2460	0.7490	0.8768	0.184*
C11	0.9849 (3)	1.3030 (5)	0.7890 (3)	0.0514 (14)
C12	0.9190 (4)	1.3693 (6)	0.7414 (4)	0.0675 (17)
H12	0.9049	1.3709	0.6874	0.081*
C13	0.8738 (5)	1.4338 (7)	0.7752 (5)	0.086 (2)
H13	0.8299	1.4799	0.7441	0.103*
C14	0.8942 (6)	1.4291 (8)	0.8536 (5)	0.088 (2)
H14	0.8632	1.4714	0.8757	0.106*
C15	0.9581 (6)	1.3647 (8)	0.9004 (5)	0.086 (2)
H15	0.9706	1.3616	0.9541	0.103*
C16	1.0046 (5)	1.3041 (6)	0.8684 (4)	0.069 (2)
H16	1.0504	1.2628	0.9011	0.082*
C17	1.0381 (4)	1.2780 (5)	0.6577 (4)	0.0501 (15)
C18	0.9862 (6)	1.2374 (7)	0.5867 (4)	0.095 (3)
H18	0.9534	1.1721	0.5849	0.114*
C19	0.9808 (9)	1.2895 (9)	0.5182 (5)	0.133 (5)
H19	0.9417	1.2645	0.4707	0.160*
C20	1.0315 (10)	1.3751 (12)	0.5202 (7)	0.131 (5)
H20	1.0335	1.4022	0.4734	0.157*
C21	1.0812 (7)	1.4258 (11)	0.5887 (9)	0.137 (5)
H21	1.1108	1.4940	0.5889	0.164*
C22	1.0865 (6)	1.3720 (8)	0.6589 (6)	0.103 (3)
H22	1.1233	1.4007	0.7065	0.124*
C23	0.8352 (3)	1.0094 (4)	0.5970 (3)	0.0417 (11)
C24	0.8079 (4)	1.0628 (7)	0.6481 (4)	0.069 (2)
H24	0.8263	1.0375	0.7000	0.083*
C25	0.7511 (5)	1.1574 (7)	0.6223 (5)	0.082 (2)
H25	0.7328	1.1950	0.6574	0.099*
C26	0.7240 (4)	1.1925 (6)	0.5474 (5)	0.075 (2)
H26	0.6867	1.2545	0.5307	0.090*
C27	0.7498 (5)	1.1401 (7)	0.4969 (4)	0.081 (2)
H27	0.7308	1.1661	0.4452	0.097*
C28	0.8054 (4)	1.0455 (6)	0.5206 (4)	0.0682 (17)
H28	0.8219	1.0076	0.4843	0.082*
C29	0.8497 (3)	0.7549 (4)	0.6028 (3)	0.0387 (10)
C30	0.7750 (4)	0.7450 (6)	0.6097 (4)	0.0586 (15)
H30	0.7545	0.8094	0.6277	0.070*
C31	0.7306 (4)	0.6421 (7)	0.5904 (4)	0.0743 (19)
H31	0.6811	0.6361	0.5966	0.089*
C32	0.7595 (5)	0.5500 (6)	0.5625 (4)	0.0723 (19)
H32	0.7284	0.4813	0.5473	0.087*
C33	0.8338 (5)	0.5557 (6)	0.5563 (4)	0.076 (2)
H33	0.8536	0.4906	0.5381	0.092*
C34	0.8791 (4)	0.6581 (5)	0.5770 (3)	0.0627 (16)
H34	0.9301	0.6617	0.5735	0.075*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ru1	0.03313 (17)	0.03417 (17)	0.03948 (18)	−0.0038 (2)	0.01610 (13)	−0.0002 (2)
P1	0.0444 (7)	0.0391 (7)	0.0533 (8)	−0.0020 (6)	0.0198 (6)	−0.0037 (6)
P2	0.0338 (8)	0.0366 (7)	0.0403 (8)	−0.0036 (6)	0.0161 (6)	−0.0012 (6)
O1	0.059 (2)	0.0356 (18)	0.064 (3)	−0.0019 (17)	0.019 (2)	0.0023 (15)
F1	0.062 (2)	0.087 (3)	0.090 (3)	0.0006 (19)	0.024 (2)	−0.019 (2)
F2	0.056 (2)	0.095 (3)	0.092 (3)	−0.0144 (19)	0.039 (2)	−0.036 (2)
F3	0.089 (4)	0.105 (4)	0.090 (4)	0.030 (3)	0.021 (3)	0.017 (3)
F4	0.072 (3)	0.093 (3)	0.153 (4)	−0.040 (2)	0.060 (3)	−0.034 (3)
F5	0.057 (2)	0.077 (2)	0.069 (2)	−0.0075 (17)	0.0288 (18)	−0.0010 (18)
F6	0.049 (2)	0.082 (3)	0.080 (3)	−0.0043 (17)	0.031 (2)	−0.0038 (19)
F7	0.066 (2)	0.094 (3)	0.128 (4)	0.012 (2)	0.035 (2)	−0.048 (3)
F8	0.074 (3)	0.160 (4)	0.067 (2)	−0.047 (3)	0.038 (2)	0.006 (2)
B1	0.039 (4)	0.066 (5)	0.070 (5)	−0.007 (3)	0.023 (3)	−0.014 (4)
B2	0.043 (4)	0.079 (5)	0.056 (4)	−0.010 (3)	0.027 (3)	−0.006 (3)
C1	0.081 (5)	0.113 (6)	0.072 (4)	0.025 (4)	0.048 (4)	0.004 (4)
C2	0.062 (5)	0.083 (5)	0.051 (4)	0.008 (3)	0.035 (4)	0.012 (3)
C3	0.050 (3)	0.064 (4)	0.056 (3)	−0.011 (3)	0.027 (3)	0.018 (3)
C4	0.064 (4)	0.045 (3)	0.047 (3)	−0.008 (3)	0.019 (3)	0.010 (2)
C5	0.055 (3)	0.044 (3)	0.049 (3)	0.003 (2)	0.016 (3)	0.007 (2)
C6	0.045 (4)	0.062 (4)	0.045 (3)	−0.004 (3)	0.011 (3)	−0.001 (3)
C7	0.073 (4)	0.061 (4)	0.035 (3)	−0.015 (3)	0.017 (3)	0.001 (2)
C8	0.073 (5)	0.069 (4)	0.070 (4)	0.023 (3)	0.019 (4)	0.009 (3)
C9	0.152 (10)	0.070 (6)	0.160 (10)	0.044 (6)	0.048 (8)	0.025 (6)
C10	0.092 (7)	0.115 (8)	0.178 (10)	0.042 (6)	0.071 (7)	0.021 (7)
C11	0.044 (3)	0.040 (3)	0.066 (4)	−0.004 (2)	0.017 (3)	−0.009 (2)
C12	0.066 (4)	0.074 (4)	0.065 (4)	0.018 (3)	0.028 (3)	0.002 (3)
C13	0.064 (5)	0.091 (6)	0.101 (6)	0.026 (4)	0.029 (4)	−0.009 (4)
C14	0.086 (6)	0.100 (6)	0.093 (6)	0.003 (5)	0.050 (5)	−0.029 (5)
C15	0.102 (7)	0.096 (6)	0.068 (5)	0.009 (5)	0.042 (5)	−0.012 (4)
C16	0.067 (5)	0.077 (5)	0.060 (4)	0.006 (4)	0.022 (4)	−0.010 (4)
C17	0.057 (4)	0.039 (3)	0.066 (4)	0.007 (3)	0.036 (3)	0.002 (3)
C18	0.158 (8)	0.070 (5)	0.056 (4)	−0.023 (5)	0.040 (5)	−0.003 (3)
C19	0.245 (15)	0.074 (6)	0.085 (6)	−0.015 (7)	0.068 (8)	−0.006 (5)
C20	0.182 (13)	0.131 (11)	0.122 (9)	0.045 (9)	0.106 (10)	0.051 (8)
C21	0.103 (8)	0.126 (9)	0.198 (13)	−0.009 (6)	0.074 (9)	0.090 (10)
C22	0.087 (6)	0.099 (6)	0.114 (7)	−0.030 (5)	0.028 (5)	0.043 (5)
C23	0.033 (3)	0.036 (3)	0.053 (3)	−0.0016 (19)	0.012 (2)	−0.001 (2)
C24	0.065 (5)	0.081 (5)	0.062 (4)	0.030 (4)	0.025 (4)	0.003 (3)
C25	0.069 (5)	0.085 (5)	0.085 (5)	0.033 (4)	0.019 (4)	−0.020 (4)
C26	0.056 (4)	0.054 (4)	0.096 (5)	0.014 (3)	0.007 (4)	−0.005 (4)
C27	0.088 (5)	0.080 (5)	0.064 (4)	0.016 (4)	0.017 (4)	0.027 (4)
C28	0.073 (5)	0.075 (4)	0.056 (4)	0.019 (4)	0.023 (3)	0.008 (3)
C29	0.039 (3)	0.037 (2)	0.039 (2)	−0.0073 (19)	0.012 (2)	−0.005 (2)
C30	0.054 (3)	0.062 (4)	0.067 (4)	−0.023 (3)	0.031 (3)	−0.008 (3)
C31	0.059 (4)	0.083 (5)	0.076 (4)	−0.030 (4)	0.020 (3)	0.001 (4)
C32	0.077 (5)	0.054 (4)	0.070 (4)	−0.026 (3)	0.010 (4)	0.000 (3)
C33	0.095 (6)	0.051 (4)	0.080 (5)	−0.012 (4)	0.031 (4)	−0.021 (3)
C34	0.059 (4)	0.064 (4)	0.072 (4)	−0.013 (3)	0.032 (3)	−0.013 (3)

Geometric parameters (Å, º)

Ru1—O1	2.107 (3)	C10—H10B	0.9600
Ru1—F6	2.135 (4)	C10—H10C	0.9600
Ru1—C4	2.159 (5)	C11—C16	1.370 (9)
Ru1—C3	2.159 (5)	C11—C12	1.383 (8)
Ru1—C5	2.186 (5)	C12—C13	1.392 (10)
Ru1—C2	2.189 (6)	C12—H12	0.9300
Ru1—C7	2.220 (5)	C13—C14	1.350 (11)
Ru1—C6	2.245 (6)	C13—H13	0.9300
Ru1—P2	2.3145 (15)	C14—C15	1.345 (12)
P1—O1	1.478 (4)	C14—H14	0.9300
P1—F1	1.554 (4)	C15—C16	1.366 (10)
P1—C11	1.792 (6)	C15—H15	0.9300
P1—C17	1.797 (6)	C16—H16	0.9300
P2—F5	1.581 (4)	C17—C22	1.359 (10)
P2—C23	1.806 (5)	C17—C18	1.361 (9)
P2—C29	1.817 (5)	C18—C19	1.364 (11)
F1—B1	1.472 (8)	C18—H18	0.9300
F2—B1	1.389 (8)	C19—C20	1.309 (17)
F3—B1	1.345 (9)	C19—H19	0.9300
F4—B1	1.360 (8)	C20—C21	1.360 (17)
F5—B2	1.485 (8)	C20—H20	0.9300
F6—B2	1.452 (8)	C21—C22	1.400 (14)
F7—B2	1.401 (8)	C21—H21	0.9300
F8—B2	1.364 (8)	C22—H22	0.9300
C1—C2	1.500 (9)	C23—C24	1.354 (9)
C1—H1A	0.9600	C23—C28	1.365 (7)
C1—H1B	0.9600	C24—C25	1.418 (9)
C1—H1C	0.9600	C24—H24	0.9300
C2—C7	1.419 (10)	C25—C26	1.339 (10)
C2—C3	1.430 (9)	C25—H25	0.9300
C3—C4	1.395 (8)	C26—C27	1.323 (10)
C3—H3	0.9300	C26—H26	0.9300
C4—C5	1.403 (8)	C27—C28	1.405 (9)
C4—H4	0.9300	C27—H27	0.9300
C5—C6	1.416 (9)	C28—H28	0.9300
C5—C8	1.501 (9)	C29—C34	1.371 (8)
C6—C7	1.360 (9)	C29—C30	1.381 (7)
C6—H6	0.9300	C30—C31	1.370 (8)
C7—H7	0.9300	C30—H30	0.9300
C8—C10	1.526 (12)	C31—C32	1.343 (10)
C8—C9	1.544 (11)	C31—H31	0.9300
C8—H8A	0.9800	C32—C33	1.365 (11)
C9—H9A	0.9600	C32—H32	0.9300
C9—H9B	0.9600	C33—C34	1.375 (9)
C9—H9C	0.9600	C33—H33	0.9300
C10—H10A	0.9600	C34—H34	0.9300
O1—Ru1—F6	81.78 (15)	C5—C6—H6	119.6
O1—Ru1—C4	165.64 (19)	Ru1—C6—H6	133.3
F6—Ru1—C4	112.55 (18)	C6—C7—C2	122.6 (6)
O1—Ru1—C3	128.1 (2)	C6—C7—Ru1	73.3 (4)
F6—Ru1—C3	148.8 (2)	C2—C7—Ru1	70.1 (3)
C4—Ru1—C3	37.7 (2)	C6—C7—H7	118.7
O1—Ru1—C5	148.56 (19)	C2—C7—H7	118.7
F6—Ru1—C5	90.82 (19)	Ru1—C7—H7	130.9
C4—Ru1—C5	37.7 (2)	C5—C8—C10	113.7 (6)
C3—Ru1—C5	68.2 (2)	C5—C8—C9	108.3 (7)
O1—Ru1—C2	97.8 (2)	C10—C8—C9	109.0 (7)
F6—Ru1—C2	164.1 (2)	C5—C8—H8A	108.6
C4—Ru1—C2	68.7 (2)	C10—C8—H8A	108.6
C3—Ru1—C2	38.4 (2)	C9—C8—H8A	108.6
C5—Ru1—C2	81.3 (2)	C8—C9—H9A	109.5
O1—Ru1—C7	93.68 (18)	C8—C9—H9B	109.5
F6—Ru1—C7	126.6 (2)	H9A—C9—H9B	109.5
C4—Ru1—C7	78.7 (2)	C8—C9—H9C	109.5
C3—Ru1—C7	67.2 (2)	H9A—C9—H9C	109.5
C5—Ru1—C7	66.4 (2)	H9B—C9—H9C	109.5
C2—Ru1—C7	37.5 (3)	C8—C10—H10A	109.5
O1—Ru1—C6	113.6 (2)	C8—C10—H10B	109.5
F6—Ru1—C6	98.8 (2)	H10A—C10—H10B	109.5
C4—Ru1—C6	66.6 (2)	C8—C10—H10C	109.5
C3—Ru1—C6	78.7 (2)	H10A—C10—H10C	109.5
C5—Ru1—C6	37.2 (2)	H10B—C10—H10C	109.5
C2—Ru1—C6	66.7 (3)	C16—C11—C12	118.8 (6)
C7—Ru1—C6	35.5 (2)	C16—C11—P1	120.7 (5)
O1—Ru1—P2	84.93 (11)	C12—C11—P1	120.4 (5)
F6—Ru1—P2	78.48 (12)	C11—C12—C13	119.3 (6)
C4—Ru1—P2	96.71 (16)	C11—C12—H12	120.4
C3—Ru1—P2	93.74 (16)	C13—C12—H12	120.4
C5—Ru1—P2	123.63 (15)	C14—C13—C12	119.6 (7)
C2—Ru1—P2	117.3 (2)	C14—C13—H13	120.2
C7—Ru1—P2	154.51 (18)	C12—C13—H13	120.2
C6—Ru1—P2	160.86 (18)	C15—C14—C13	121.6 (8)
O1—P1—F1	115.5 (2)	C15—C14—H14	119.2
O1—P1—C11	110.1 (3)	C13—C14—H14	119.2
F1—P1—C11	103.9 (2)	C14—C15—C16	119.5 (7)
O1—P1—C17	108.4 (3)	C14—C15—H15	120.2
F1—P1—C17	109.4 (3)	C16—C15—H15	120.2
C11—P1—C17	109.3 (3)	C11—C16—C15	121.1 (7)
F5—P2—C23	105.6 (2)	C11—C16—H16	119.5
F5—P2—C29	104.2 (2)	C15—C16—H16	119.5
C23—P2—C29	105.3 (2)	C22—C17—C18	118.0 (7)
F5—P2—Ru1	106.39 (16)	C22—C17—P1	121.5 (6)
C23—P2—Ru1	115.38 (17)	C18—C17—P1	120.5 (5)
C29—P2—Ru1	118.74 (17)	C17—C18—C19	121.9 (8)
P1—O1—Ru1	147.6 (3)	C17—C18—H18	119.0
B1—F1—P1	134.7 (4)	C19—C18—H18	119.0
B2—F5—P2	120.2 (4)	C20—C19—C18	119.1 (11)
B2—F6—Ru1	121.5 (3)	C20—C19—H19	120.4
F3—B1—F4	112.2 (6)	C18—C19—H19	120.4
F3—B1—F2	110.2 (6)	C19—C20—C21	122.1 (10)
F4—B1—F2	109.1 (6)	C19—C20—H20	119.0
F3—B1—F1	107.9 (6)	C21—C20—H20	119.0
F4—B1—F1	107.6 (6)	C20—C21—C22	117.9 (10)
F2—B1—F1	109.8 (5)	C20—C21—H21	121.0
F8—B2—F7	109.5 (6)	C22—C21—H21	121.0
F8—B2—F6	112.2 (5)	C17—C22—C21	120.2 (10)
F7—B2—F6	108.9 (6)	C17—C22—H22	119.9
F8—B2—F5	108.5 (5)	C21—C22—H22	119.9
F7—B2—F5	107.7 (5)	C24—C23—C28	119.1 (5)
F6—B2—F5	109.9 (5)	C24—C23—P2	121.1 (5)
C2—C1—H1A	109.5	C28—C23—P2	119.8 (4)
C2—C1—H1B	109.5	C23—C24—C25	119.8 (7)
H1A—C1—H1B	109.5	C23—C24—H24	120.1
C2—C1—H1C	109.5	C25—C24—H24	120.1
H1A—C1—H1C	109.5	C26—C25—C24	119.9 (7)
H1B—C1—H1C	109.5	C26—C25—H25	120.1
C7—C2—C3	116.5 (6)	C24—C25—H25	120.1
C7—C2—C1	122.5 (7)	C27—C26—C25	120.7 (6)
C3—C2—C1	120.9 (7)	C27—C26—H26	119.6
C7—C2—Ru1	72.4 (4)	C25—C26—H26	119.6
C3—C2—Ru1	69.7 (3)	C26—C27—C28	120.7 (6)
C1—C2—Ru1	131.1 (5)	C26—C27—H27	119.7
C4—C3—C2	120.6 (6)	C28—C27—H27	119.7
C4—C3—Ru1	71.1 (3)	C23—C28—C27	119.8 (6)
C2—C3—Ru1	71.9 (3)	C23—C28—H28	120.1
C4—C3—H3	119.7	C27—C28—H28	120.1
C2—C3—H3	119.7	C34—C29—C30	118.1 (5)
Ru1—C3—H3	129.8	C34—C29—P2	120.1 (4)
C3—C4—C5	121.2 (5)	C30—C29—P2	121.7 (4)
C3—C4—Ru1	71.2 (3)	C31—C30—C29	121.4 (6)
C5—C4—Ru1	72.2 (3)	C31—C30—H30	119.3
C3—C4—H4	119.4	C29—C30—H30	119.3
C5—C4—H4	119.4	C32—C31—C30	119.3 (7)
Ru1—C4—H4	129.7	C32—C31—H31	120.4
C4—C5—C6	118.1 (6)	C30—C31—H31	120.4
C4—C5—C8	119.6 (5)	C31—C32—C33	121.1 (6)
C6—C5—C8	122.3 (6)	C31—C32—H32	119.5
C4—C5—Ru1	70.1 (3)	C33—C32—H32	119.5
C6—C5—Ru1	73.6 (4)	C32—C33—C34	119.7 (7)
C8—C5—Ru1	129.0 (4)	C32—C33—H33	120.1
C7—C6—C5	120.8 (6)	C34—C33—H33	120.1
C7—C6—Ru1	71.3 (4)	C29—C34—C33	120.4 (6)
C5—C6—Ru1	69.1 (3)	C29—C34—H34	119.8
C7—C6—H6	119.6	C33—C34—H34	119.8