Chloro(1-{3-[2-(di­phenyl­phos­phanyl-[kappa]P)­ethyl]-[eta]⁶-benzyl}-3,5-di­methyl-1H-pyrazole-[kappa]N²)­ruthenium(II) tri­fluoro­methane­sulfonate

To address the question of the role of chirality at the metal in enantioselective catalysis, a pseudo-tetrahedral three-legged piano-stool complex has been prepared, i.e. [RuCl(C₂₆H₂₇N₂P)](CF₃SO₃). Anchoring a phosphine and a pyrazole tether to an arene (PArN) yields, after [eta]⁶:[eta]¹:[eta]¹ coordination to ruthenium, [{[eta]⁶:[eta]¹:[eta]¹-(PArN)}RuCl]⁺ as a 1:1 mixture of enantiomers. Unfortunately, all attempts to resolve the enantiomers failed. The structure solution revealed the presence of racemic crystals.

S1. Comment

NO COMMENT

S2. Experimental

The synthesis of the ParN(CH₃) ligand, i.e. 1-{3-[2-(diphenylphosphanyl)ethyl]benzyl}-3,5-dimethyl-1H-pyrazole, is analogous to the synthesis of PArN(CF₃) (Therrien & Ward, 1999). Replacing the bis(trifluoromethyl)pyrazole by 3,5-dimethylpyrazole affords the corresponding ligand. Only its coordination to ruthenium is fully described. To a dichloromethane solution (25 ml) of [RuCl₂(η⁶-C₆H₅CO₂Et)]₂ (0.129 g, 0.20 mmol), PArN(CH₃) (0.160 g, 0.40 mmol) was added. The mixture was stirred for 20 min. The volume was reduced to 10 ml and the product precipitated with hexane to afford quantitatively [RuCl₂(η⁶-C₆H₅CO₂Et){η¹-ParN(CH₃)}]. ¹H NMR (CDCl₃): 7.9–7.8 (m, 4H), 7.52 (m, 6H), 7.04 (t, 1H), 6.84 (m, 1H), 6.71 (s, 2H), 6.34 (d, 2H), 5.79 (s, 1H), 5.46 (s, 1H), 5.06 (s, 4H), 4.30 (m, 2H), 2.86 (m, 2H), 2.39 (m, 2H), 2.19 (s, 3H), 2.16 (s, 3H), 1.34 p.p.m. (t, 3H). ³¹P{¹H} NMR (CDCl₃): 23.2 p.p.m. Into a 25 ml pressure Schlenk flask was introduced [RuCl₂(η⁶-C₆H₅CO₂Et){η¹-ParN(CH₃)}] (0.180 g, 0.25 mmol) in dichloromethane (10 ml). After three freeze–pump–thaw cycles, the solution was heated at 393 K for 48 h, cooled to room temperature and the product precipitated with hexane (200 ml). The yellow–orange solid was filtered off and washed with ether. Purification by flash chromatography with CH₂Cl₂–MeOH (20:1), yielded [RuCl₂{η⁶:η¹-ParN(CH₃)}] (0.038 g, 0.07 mmol, 27%). ¹H NMR (CDCl₃): 7.82 (m, 2H), 7.64 (m, 2H), 7.39 (m, 6H), 5.89 (dd, 1H), 5.85 (s, 1H), 5.71 (d, 1H), 5.36 (d, 1H), 5.16 (d, 1H), 5.03 (d, 1H), 4.68 (s, 1H), 3.49 (m, 2H), 2.53 (m, 2H), 1.64 (s, 3H), 1.27 p.p.m. (s, 3H). ³¹P {¹H} NMR (CDCl₃) 46.2 p.p.m. To a CHCl₃ solution (5 ml) of [RuCl₂{η⁶:η¹-ParN(CH₃)}] (300 mg, 0.51 mmol), AgOSO₂CF₃ (180 mg, 0.51 mmol) was added. The mixture was stirred at room temperature for 24 h. After filtration through Celite, the solution was evaporated to dryness to afford quantitatively [RuCl{η⁶:η¹:η¹-ParN(CH₃)}](OSO₂CF₃). After a week at room temperature in CHCl₃, crystals suitable for X-ray analysis were obtained. ¹H NMR (CDCl₃): 8.03 (m, 2H), 7.7–7.1 (m, 8H), 6.79 (s, 1H), 6.33 (br, 1H), 6.21 (d, 1H), 5.66 (s, 1H), 5.53 (d, 1H), 5.18 (d, 1H), 4.69 (d, 1H), 3.81 (m, 1H), 3.48 (m, 1H), 3.18 (m, 1H), 2.91 (m, 1H), 1.44 (s, 3H), 1.26 p.p.m (s, 3H). ³¹P {¹H} NMR (CDCl₃): 47.4 p.p.m.

Computing details

Data collection: SMART (Siemens 1994-1996); cell refinement: SAINT (Siemens 1994-1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97.

Chloro[eta⁶:eta¹:eta¹-{1-(3-(2-(diphenylphosphanyl)ethyl)benzyl) −3,5-dimethyl-1H-pyrazole}]ruthenium(II) trifluoromethanesulfonate

Crystal data

[RuCl(C26H27N2P)](CF3O3S)	Z = 2
Mr = 684.06	F(000) = 692
Triclinic, P1	Dx = 1.637 Mg m^−3
a = 9.3674 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.0111 (3) Å	Cell parameters from 3988 reflections
c = 13.6724 (4) Å	θ = 1.5–26.4°
α = 94.198 (1)°	µ = 0.85 mm^−1
β = 92.139 (1)°	T = 293 K
γ = 98.968 (1)°	Plate, orange
V = 1387.57 (7) Å^3	0.42 × 0.11 × 0.08 mm

Data collection

Siemens SMART CCD diffractometer	4074 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.039
Graphite monochromator	θmax = 26.4°, θmin = 1.5°
ω scans, 1271 frames, 0.30°, 20 s, detector distance 5.5 cm, detector angle 23.0°	h = −11→11
6978 measured reflections	k = −13→7
5008 independent reflections	l = −16→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.120	H-atom parameters constrained
S = 1.18	w = 1/[σ^2(Fo^2) + (0.0109P)^2 + 4.6884P] where P = (Fo^2 + 2Fc^2)/3
5008 reflections	(Δ/σ)max < 0.001
356 parameters	Δρmax = 0.54 e Å^−3
0 restraints	Δρmin = −0.84 e Å^−3

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 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
Ru	0.28061 (5)	0.53426 (4)	0.34516 (3)	0.03414 (14)
Cl	0.52847 (15)	0.62669 (15)	0.33011 (11)	0.0512 (4)
P	0.20802 (15)	0.54235 (13)	0.17773 (9)	0.0348 (3)
N1	0.3021 (5)	0.2854 (4)	0.4089 (3)	0.0427 (11)
N2	0.3510 (5)	0.3600 (4)	0.3362 (3)	0.0390 (10)
C1	0.0675 (6)	0.5895 (6)	0.3587 (4)	0.0432 (14)
C2	0.0639 (6)	0.4695 (6)	0.3903 (4)	0.0422 (13)
H2	−0.0078	0.4057	0.3650	0.065 (5)*
C3	0.1702 (6)	0.4466 (6)	0.4609 (4)	0.0413 (13)
C4	0.2707 (7)	0.5478 (6)	0.5084 (4)	0.0494 (15)
H4	0.3343	0.5349	0.5590	0.065 (5)*
C5	0.2708 (7)	0.6647 (6)	0.4771 (4)	0.0512 (15)
H5	0.3380	0.7299	0.5059	0.065 (5)*
C6	0.1721 (7)	0.6878 (6)	0.4029 (4)	0.0503 (15)
H6	0.1752	0.7671	0.3830	0.065 (5)*
C7	−0.0270 (6)	0.6074 (6)	0.2709 (4)	0.0494 (15)
H7A	−0.0104	0.6933	0.2565	0.072 (6)*
H7B	−0.1281	0.5853	0.2849	0.072 (6)*
C8	0.0092 (6)	0.5254 (6)	0.1818 (4)	0.0432 (13)
H8A	−0.0316	0.5506	0.1218	0.072 (6)*
H8B	−0.0313	0.4399	0.1883	0.072 (6)*
C9	0.1901 (6)	0.3161 (6)	0.4731 (4)	0.0475 (14)
H9A	0.2184	0.3072	0.5409	0.072 (6)*
H9B	0.1000	0.2608	0.4561	0.072 (6)*
C10	0.3640 (7)	0.1833 (6)	0.4080 (5)	0.0509 (15)
C11	0.4561 (7)	0.1902 (6)	0.3326 (5)	0.0536 (16)
H11	0.5147	0.1326	0.3139	0.065 (5)*
C12	0.4464 (6)	0.2992 (6)	0.2888 (4)	0.0449 (14)
C13	0.3299 (9)	0.0877 (7)	0.4778 (6)	0.079 (2)
H13A	0.3689	0.1195	0.5422	0.072 (6)*
H13B	0.3719	0.0164	0.4572	0.072 (6)*
H13C	0.2269	0.0651	0.4794	0.072 (6)*
C14	0.5298 (7)	0.3481 (7)	0.2047 (5)	0.0599 (18)
H14A	0.5028	0.4257	0.1903	0.072 (6)*
H14B	0.5085	0.2904	0.1479	0.072 (6)*
H14C	0.6316	0.3594	0.2220	0.072 (6)*
C21	0.2569 (6)	0.6906 (5)	0.1248 (4)	0.0404 (13)
C22	0.1913 (7)	0.7093 (6)	0.0346 (5)	0.0574 (17)
H22	0.1235	0.6470	0.0026	0.065 (5)*
C23	0.2268 (9)	0.8193 (7)	−0.0066 (5)	0.071 (2)
H23	0.1832	0.8313	−0.0666	0.065 (5)*
C24	0.3260 (9)	0.9112 (7)	0.0404 (6)	0.072 (2)
H24	0.3509	0.9852	0.0120	0.065 (5)*
C25	0.3886 (8)	0.8944 (6)	0.1290 (6)	0.0674 (19)
H25	0.4546	0.9579	0.1612	0.065 (5)*
C26	0.3552 (7)	0.7841 (6)	0.1716 (5)	0.0514 (15)
H26	0.3991	0.7734	0.2318	0.065 (5)*
C31	0.2338 (5)	0.4236 (5)	0.0827 (4)	0.0348 (12)
C32	0.1731 (7)	0.3025 (6)	0.0944 (5)	0.0520 (15)
H32	0.1216	0.2842	0.1497	0.065 (5)*
C33	0.1883 (7)	0.2094 (6)	0.0250 (6)	0.0649 (19)
H33	0.1449	0.1290	0.0327	0.065 (5)*
C34	0.2684 (7)	0.2348 (7)	−0.0571 (5)	0.0623 (19)
H34	0.2794	0.1717	−0.1039	0.065 (5)*
C35	0.3304 (7)	0.3537 (7)	−0.0679 (4)	0.0583 (17)
H35	0.3849	0.3712	−0.1221	0.065 (5)*
C36	0.3128 (6)	0.4489 (6)	0.0014 (4)	0.0458 (14)
H36	0.3544	0.5295	−0.0072	0.065 (5)*
S1	0.14987 (18)	−0.11042 (15)	0.70187 (13)	0.0549 (4)
O1	0.0983 (8)	−0.2212 (5)	0.7453 (4)	0.100 (2)
O2	0.2804 (6)	−0.0435 (6)	0.7448 (6)	0.119 (3)
O3	0.1357 (8)	−0.1263 (6)	0.5984 (4)	0.109 (2)
C	0.0245 (10)	−0.0115 (10)	0.7355 (8)	0.098 (3)
F1	0.0470 (12)	0.0912 (7)	0.6964 (7)	0.212 (5)
F2	−0.1127 (7)	−0.0680 (8)	0.7167 (7)	0.187 (4)
F3	0.0272 (7)	0.0162 (7)	0.8308 (5)	0.144 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ru	0.0325 (2)	0.0433 (3)	0.0263 (2)	0.00672 (18)	0.00182 (16)	−0.00048 (17)
Cl	0.0369 (8)	0.0670 (10)	0.0472 (8)	−0.0018 (7)	−0.0034 (6)	0.0127 (7)
P	0.0354 (7)	0.0411 (8)	0.0272 (7)	0.0056 (6)	−0.0012 (5)	0.0007 (6)
N1	0.041 (3)	0.047 (3)	0.040 (3)	0.005 (2)	0.002 (2)	0.009 (2)
N2	0.034 (2)	0.050 (3)	0.034 (2)	0.008 (2)	0.0016 (19)	0.002 (2)
C1	0.038 (3)	0.054 (4)	0.039 (3)	0.015 (3)	0.008 (2)	−0.008 (3)
C2	0.031 (3)	0.060 (4)	0.037 (3)	0.010 (3)	0.015 (2)	0.000 (3)
C3	0.038 (3)	0.059 (4)	0.028 (3)	0.010 (3)	0.013 (2)	0.005 (3)
C4	0.048 (4)	0.075 (4)	0.025 (3)	0.014 (3)	0.005 (2)	−0.008 (3)
C5	0.058 (4)	0.056 (4)	0.037 (3)	0.010 (3)	0.000 (3)	−0.015 (3)
C6	0.053 (4)	0.055 (4)	0.044 (3)	0.017 (3)	−0.001 (3)	−0.008 (3)
C7	0.041 (3)	0.060 (4)	0.049 (3)	0.021 (3)	−0.005 (3)	−0.006 (3)
C8	0.037 (3)	0.057 (4)	0.035 (3)	0.010 (3)	−0.006 (2)	−0.003 (3)
C9	0.045 (3)	0.060 (4)	0.039 (3)	0.006 (3)	0.010 (3)	0.014 (3)
C10	0.045 (4)	0.048 (4)	0.059 (4)	0.006 (3)	−0.008 (3)	0.006 (3)
C11	0.046 (4)	0.052 (4)	0.064 (4)	0.021 (3)	−0.009 (3)	−0.008 (3)
C12	0.040 (3)	0.055 (4)	0.040 (3)	0.014 (3)	−0.005 (2)	−0.005 (3)
C13	0.080 (6)	0.058 (5)	0.099 (6)	0.011 (4)	−0.007 (5)	0.024 (4)
C14	0.052 (4)	0.086 (5)	0.047 (4)	0.026 (4)	0.009 (3)	0.000 (3)
C21	0.040 (3)	0.042 (3)	0.040 (3)	0.010 (3)	0.000 (2)	0.004 (2)
C22	0.065 (4)	0.059 (4)	0.047 (4)	0.009 (3)	−0.017 (3)	0.011 (3)
C23	0.084 (6)	0.078 (5)	0.056 (4)	0.023 (4)	−0.003 (4)	0.026 (4)
C24	0.075 (5)	0.065 (5)	0.083 (5)	0.017 (4)	0.016 (4)	0.035 (4)
C25	0.063 (5)	0.051 (4)	0.084 (5)	−0.003 (3)	−0.001 (4)	0.011 (4)
C26	0.056 (4)	0.047 (4)	0.048 (4)	−0.003 (3)	−0.005 (3)	0.011 (3)
C31	0.030 (3)	0.044 (3)	0.030 (3)	0.007 (2)	0.001 (2)	−0.004 (2)
C32	0.049 (4)	0.049 (4)	0.056 (4)	0.004 (3)	0.019 (3)	0.000 (3)
C33	0.058 (4)	0.042 (4)	0.091 (5)	0.002 (3)	0.017 (4)	−0.010 (4)
C34	0.058 (4)	0.064 (5)	0.061 (4)	0.011 (3)	0.008 (3)	−0.025 (4)
C35	0.057 (4)	0.079 (5)	0.040 (3)	0.013 (4)	0.010 (3)	0.000 (3)
C36	0.043 (3)	0.054 (4)	0.040 (3)	0.006 (3)	0.002 (3)	0.002 (3)
S1	0.0535 (10)	0.0494 (9)	0.0612 (10)	0.0063 (8)	0.0099 (8)	0.0009 (8)
O1	0.144 (6)	0.058 (3)	0.094 (4)	−0.002 (4)	0.016 (4)	0.013 (3)
O2	0.048 (3)	0.110 (5)	0.186 (7)	0.002 (3)	−0.010 (4)	−0.042 (5)
O3	0.177 (7)	0.085 (4)	0.062 (4)	0.004 (4)	0.035 (4)	−0.002 (3)
C	0.070 (6)	0.100 (7)	0.117 (8)	0.022 (5)	−0.036 (5)	−0.034 (6)
F1	0.337 (13)	0.104 (5)	0.231 (9)	0.126 (7)	0.025 (8)	0.053 (6)
F2	0.074 (4)	0.222 (8)	0.251 (9)	0.046 (5)	−0.057 (5)	−0.095 (7)
F3	0.104 (4)	0.167 (6)	0.145 (6)	0.012 (4)	0.023 (4)	−0.087 (5)

Geometric parameters (Å, º)

Ru—N2	2.121 (5)	C7—C8	1.543 (8)
Ru—C3	2.131 (5)	C10—C11	1.368 (9)
Ru—C2	2.172 (5)	C10—C13	1.479 (9)
Ru—C1	2.186 (5)	C11—C12	1.392 (9)
Ru—C6	2.218 (6)	C12—C14	1.501 (8)
Ru—C4	2.232 (5)	C21—C26	1.372 (8)
Ru—C5	2.236 (5)	C21—C22	1.400 (8)
Ru—P	2.3755 (13)	C22—C23	1.372 (9)
Ru—Cl	2.4081 (15)	C23—C24	1.367 (10)
P—C31	1.824 (5)	C24—C25	1.363 (10)
P—C21	1.834 (6)	C25—C26	1.382 (9)
P—C8	1.846 (6)	C31—C36	1.380 (7)
N1—C10	1.341 (8)	C31—C32	1.389 (8)
N1—N2	1.381 (6)	C32—C33	1.373 (9)
N1—C9	1.458 (7)	C33—C34	1.394 (10)
N2—C12	1.354 (7)	C34—C35	1.368 (9)
C1—C2	1.416 (8)	C35—C36	1.394 (8)
C1—C6	1.424 (8)	S1—O2	1.408 (6)
C1—C7	1.508 (8)	S1—O3	1.412 (6)
C2—C3	1.425 (8)	S1—O1	1.420 (6)
C3—C4	1.439 (8)	S1—C	1.772 (10)
C3—C9	1.498 (8)	C—F1	1.277 (12)
C4—C5	1.386 (9)	C—F3	1.315 (11)
C5—C6	1.411 (8)	C—F2	1.345 (11)
N2—Ru—C3	78.03 (19)	C1—C2—Ru	71.6 (3)
N2—Ru—C2	96.5 (2)	C3—C2—Ru	69.1 (3)
C3—Ru—C2	38.7 (2)	C2—C3—C4	119.9 (6)
N2—Ru—C1	132.8 (2)	C2—C3—C9	118.9 (5)
C3—Ru—C1	69.4 (2)	C4—C3—C9	120.5 (5)
C2—Ru—C1	37.9 (2)	C2—C3—Ru	72.2 (3)
N2—Ru—C6	158.9 (2)	C4—C3—Ru	74.6 (3)
C3—Ru—C6	81.0 (2)	C9—C3—Ru	116.6 (4)
C2—Ru—C6	67.8 (2)	C5—C4—C3	118.7 (5)
C1—Ru—C6	37.7 (2)	C5—C4—Ru	72.1 (3)
N2—Ru—C4	94.9 (2)	C3—C4—Ru	67.0 (3)
C3—Ru—C4	38.4 (2)	C4—C5—C6	121.9 (6)
C2—Ru—C4	68.5 (2)	C4—C5—Ru	71.8 (3)
C1—Ru—C4	80.5 (2)	C6—C5—Ru	70.8 (3)
C6—Ru—C4	66.7 (2)	C5—C6—C1	119.9 (6)
N2—Ru—C5	129.1 (2)	C5—C6—Ru	72.3 (3)
C3—Ru—C5	67.6 (2)	C1—C6—Ru	69.9 (3)
C2—Ru—C5	79.5 (2)	C1—C7—C8	109.1 (5)
C1—Ru—C5	67.4 (2)	C7—C8—P	108.0 (4)
C6—Ru—C5	36.9 (2)	N1—C9—C3	108.4 (4)
C4—Ru—C5	36.1 (2)	N1—C10—C11	106.1 (5)
N2—Ru—P	99.37 (12)	N1—C10—C13	123.1 (6)
C3—Ru—P	130.90 (16)	C11—C10—C13	130.8 (6)
C2—Ru—P	94.72 (15)	C10—C11—C12	107.7 (5)
C1—Ru—P	78.72 (15)	N2—C12—C11	109.5 (5)
C6—Ru—P	96.12 (16)	N2—C12—C14	123.3 (5)
C4—Ru—P	159.18 (16)	C11—C12—C14	127.2 (6)
C5—Ru—P	131.49 (17)	C26—C21—C22	119.1 (6)
N2—Ru—Cl	87.89 (13)	C26—C21—P	121.7 (4)
C3—Ru—Cl	132.60 (16)	C22—C21—P	119.2 (5)
C2—Ru—Cl	167.79 (15)	C23—C22—C21	120.2 (6)
C1—Ru—Cl	139.33 (17)	C24—C23—C22	120.1 (7)
C6—Ru—Cl	104.78 (17)	C25—C24—C23	120.1 (7)
C4—Ru—Cl	99.86 (16)	C24—C25—C26	120.9 (7)
C5—Ru—Cl	88.90 (17)	C21—C26—C25	119.7 (6)
P—Ru—Cl	95.78 (5)	C36—C31—C32	119.0 (5)
C31—P—C21	106.3 (2)	C36—C31—P	122.8 (4)
C31—P—C8	102.9 (2)	C32—C31—P	118.1 (4)
C21—P—C8	103.3 (3)	C33—C32—C31	120.7 (6)
C31—P—Ru	122.47 (18)	C32—C33—C34	120.3 (6)
C21—P—Ru	116.70 (18)	C35—C34—C33	119.1 (6)
C8—P—Ru	102.35 (18)	C34—C35—C36	120.7 (6)
C10—N1—N2	112.2 (5)	C31—C36—C35	120.1 (6)
C10—N1—C9	126.4 (5)	O2—S1—O3	117.6 (5)
N2—N1—C9	121.3 (5)	O2—S1—O1	115.1 (5)
C12—N2—N1	104.5 (5)	O3—S1—O1	111.7 (4)
C12—N2—Ru	140.4 (4)	O2—S1—C	101.6 (4)
N1—N2—Ru	114.4 (3)	O3—S1—C	104.7 (5)
C2—C1—C6	119.3 (5)	O1—S1—C	103.8 (5)
C2—C1—C7	119.2 (5)	F1—C—F3	106.1 (9)
C6—C1—C7	121.2 (6)	F1—C—F2	111.0 (9)
C2—C1—Ru	70.5 (3)	F3—C—F2	101.9 (10)
C6—C1—Ru	72.4 (3)	F1—C—S1	113.1 (9)
C7—C1—Ru	122.7 (4)	F3—C—S1	112.6 (7)
C1—C2—C3	120.0 (5)	F2—C—S1	111.4 (7)