Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102018395/gd1228sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102018395/gd1228Isup2.hkl |
CCDC reference: 199412
Compound (I) was synthesized by reaction of the (+)-EPHOS ligand (2.670 g, 5 mmol) with CpRu(PPh3)2Cl (1.815 g, 2.5 mmol) in refluxing toluene (20 ml) for 18 h. Purification of the crude product by flash chromatography (CH2Cl2) afforded pure (I) (1.164 g, 63%) as an orange solid. Recrystallization from a dichloromethane-hexane mixture (1:1) afforded orange crystals Please clarify - blue given below suitable for X-ray analysis.
H atoms were treated as riding, with C—H distances in the range 0.93–0.98 Å. Is this added text OK?
Data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SHELXTL (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. A view of the molecular structure of complex (I). Displacement ellipsoids are shown at the 30% probability level and H atoms have been omitted for clarity. |
[Ru(C5H5)Cl(C34H33NOP2)] | F(000) = 1512 |
Mr = 735.16 | Dx = 1.375 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 14894 reflections |
a = 13.2734 (1) Å | θ = 1.8–30.0° |
b = 14.3376 (1) Å | µ = 0.64 mm−1 |
c = 18.6640 (2) Å | T = 296 K |
V = 3551.92 (5) Å3 | Parallelepiped, blue |
Z = 4 | 0.30 × 0.28 × 0.14 mm |
Make Model CCD area-detector diffractometer | 9351 independent reflections |
Radiation source: fine-focus sealed tube | 6619 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.044 |
ϕ and ω scans | θmax = 30.0°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −18→13 |
Tmin = 0.832, Tmax = 0.916 | k = −18→19 |
25398 measured reflections | l = −22→24 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.038 | w = 1/[σ2(Fo2) + (0.0316P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.078 | (Δ/σ)max = 0.015 |
S = 1.01 | Δρmax = 0.37 e Å−3 |
9351 reflections | Δρmin = −0.59 e Å−3 |
409 parameters | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.00095 (12) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), with 3652 Friedel pairs Query |
Secondary atom site location: difference Fourier map | Absolute structure parameter: −0.03 (2) |
[Ru(C5H5)Cl(C34H33NOP2)] | V = 3551.92 (5) Å3 |
Mr = 735.16 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 13.2734 (1) Å | µ = 0.64 mm−1 |
b = 14.3376 (1) Å | T = 296 K |
c = 18.6640 (2) Å | 0.30 × 0.28 × 0.14 mm |
Make Model CCD area-detector diffractometer | 9351 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 6619 reflections with I > 2σ(I) |
Tmin = 0.832, Tmax = 0.916 | Rint = 0.044 |
25398 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | H-atom parameters constrained |
wR(F2) = 0.078 | Δρmax = 0.37 e Å−3 |
S = 1.01 | Δρmin = −0.59 e Å−3 |
9351 reflections | Absolute structure: Flack (1983), with 3652 Friedel pairs Query |
409 parameters | Absolute structure parameter: −0.03 (2) |
0 restraints |
Experimental. NMR data for (I). 31P NMR (162 MHz, CDCl3): 141.6 (d, J = 69.3 Hz), 116.4 (d, J = 69.3 Hz). 1H NMR (400 MHz, CDCl3): 8.09 (m, 2H), 7.80 (m, 2H), 7.6–7.1 (m, 17H), 7.07 (t, J = 7.2 Hz, 2H), 6.94 (d, J = 7.2 Hz, 2H), 5.42 (m, 1H), 4.60 (bs, 1H), 4.09 (s, 5H), 1.84 (d, J = 7.6 Hz, 3H), 1.03 (d, J = 6.8 Hz, 3H). |
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. |
x | y | z | Uiso*/Ueq | ||
Ru | 0.229564 (19) | 0.152984 (16) | 0.790951 (14) | 0.04018 (7) | |
P1 | 0.35701 (6) | 0.24549 (5) | 0.74856 (4) | 0.03655 (17) | |
P2 | 0.11931 (5) | 0.20328 (5) | 0.70658 (5) | 0.03585 (16) | |
Cl | 0.18925 (7) | 0.26810 (6) | 0.88273 (5) | 0.0595 (2) | |
O | 0.15088 (16) | 0.28621 (13) | 0.65111 (11) | 0.0410 (5) | |
N | 0.33216 (17) | 0.35627 (16) | 0.72425 (13) | 0.0414 (6) | |
C1 | 0.4254 (2) | 0.1981 (2) | 0.67102 (18) | 0.0471 (8) | |
C2 | 0.3710 (3) | 0.1468 (3) | 0.62076 (19) | 0.0629 (10) | |
H2 | 0.3035 | 0.1334 | 0.6291 | 0.075* | |
C3 | 0.4168 (4) | 0.1155 (4) | 0.5585 (2) | 0.0898 (15) | |
H3 | 0.3794 | 0.0826 | 0.5248 | 0.108* | |
C4 | 0.5170 (4) | 0.1328 (4) | 0.5463 (3) | 0.1032 (18) | |
H4 | 0.5476 | 0.1109 | 0.5048 | 0.124* | |
C5 | 0.5708 (4) | 0.1817 (4) | 0.5946 (3) | 0.1038 (19) | |
H5 | 0.6388 | 0.1931 | 0.5864 | 0.125* | |
C6 | 0.5257 (3) | 0.2151 (3) | 0.6564 (2) | 0.0737 (12) | |
H6 | 0.5638 | 0.2496 | 0.6888 | 0.088* | |
C7 | 0.4569 (2) | 0.2556 (2) | 0.81635 (16) | 0.0438 (8) | |
C8 | 0.5259 (3) | 0.1846 (3) | 0.8276 (2) | 0.0586 (10) | |
H8 | 0.5280 | 0.1345 | 0.7961 | 0.070* | |
C9 | 0.5919 (3) | 0.1872 (3) | 0.8853 (2) | 0.0737 (12) | |
H9 | 0.6369 | 0.1384 | 0.8926 | 0.088* | |
C10 | 0.5912 (3) | 0.2608 (4) | 0.9310 (2) | 0.0822 (14) | |
H10 | 0.6352 | 0.2624 | 0.9698 | 0.099* | |
C11 | 0.5242 (3) | 0.3335 (4) | 0.9193 (2) | 0.0883 (14) | |
H11 | 0.5244 | 0.3845 | 0.9500 | 0.106* | |
C12 | 0.4570 (3) | 0.3312 (3) | 0.8627 (2) | 0.0645 (11) | |
H12 | 0.4120 | 0.3801 | 0.8558 | 0.077* | |
C13 | 0.2312 (2) | 0.39628 (18) | 0.73452 (15) | 0.0376 (6) | |
H13 | 0.2003 | 0.3611 | 0.7738 | 0.045* | |
C14 | 0.1614 (2) | 0.38363 (19) | 0.66942 (17) | 0.0397 (7) | |
H14 | 0.0946 | 0.4079 | 0.6820 | 0.048* | |
C15 | 0.1954 (2) | 0.4311 (2) | 0.60154 (17) | 0.0435 (8) | |
C16 | 0.2613 (3) | 0.3889 (2) | 0.55473 (18) | 0.0554 (9) | |
H16 | 0.2849 | 0.3293 | 0.5649 | 0.066* | |
C17 | 0.2934 (3) | 0.4335 (3) | 0.4925 (2) | 0.0740 (12) | |
H17 | 0.3377 | 0.4037 | 0.4614 | 0.089* | |
C18 | 0.2595 (4) | 0.5210 (3) | 0.4774 (2) | 0.0840 (14) | |
H18 | 0.2817 | 0.5512 | 0.4361 | 0.101* | |
C19 | 0.1936 (4) | 0.5649 (3) | 0.5221 (2) | 0.0790 (14) | |
H19 | 0.1703 | 0.6243 | 0.5109 | 0.095* | |
C20 | 0.1605 (3) | 0.5201 (2) | 0.5853 (2) | 0.0609 (10) | |
H20 | 0.1157 | 0.5500 | 0.6160 | 0.073* | |
C21 | −0.0096 (2) | 0.2360 (2) | 0.73185 (18) | 0.0463 (8) | |
C22 | −0.0778 (3) | 0.2623 (2) | 0.6790 (2) | 0.0617 (10) | |
H22 | −0.0561 | 0.2671 | 0.6318 | 0.074* | |
C23 | −0.1772 (3) | 0.2812 (2) | 0.6953 (3) | 0.0743 (13) | |
H23 | −0.2221 | 0.2978 | 0.6592 | 0.089* | |
C24 | −0.2094 (3) | 0.2754 (3) | 0.7654 (3) | 0.0787 (14) | |
H24 | −0.2762 | 0.2885 | 0.7767 | 0.094* | |
C25 | −0.1438 (3) | 0.2506 (3) | 0.8181 (3) | 0.0761 (12) | |
H25 | −0.1659 | 0.2471 | 0.8653 | 0.091* | |
C26 | −0.0431 (3) | 0.2305 (2) | 0.8016 (2) | 0.0573 (9) | |
H26 | 0.0013 | 0.2133 | 0.8378 | 0.069* | |
C27 | 0.0879 (2) | 0.1185 (2) | 0.63631 (18) | 0.0438 (8) | |
C28 | 0.0351 (3) | 0.0382 (2) | 0.6554 (2) | 0.0592 (10) | |
H28 | 0.0145 | 0.0299 | 0.7025 | 0.071* | |
C29 | 0.0130 (3) | −0.0297 (3) | 0.6044 (3) | 0.0756 (13) | |
H29 | −0.0213 | −0.0836 | 0.6176 | 0.091* | |
C30 | 0.0419 (4) | −0.0167 (3) | 0.5345 (3) | 0.0924 (16) | |
H30 | 0.0268 | −0.0617 | 0.5003 | 0.111* | |
C31 | 0.0932 (4) | 0.0628 (4) | 0.5148 (3) | 0.0933 (16) | |
H31 | 0.1124 | 0.0716 | 0.4674 | 0.112* | |
C32 | 0.1159 (3) | 0.1293 (3) | 0.5656 (2) | 0.0613 (10) | |
H32 | 0.1508 | 0.1826 | 0.5519 | 0.074* | |
C33 | 0.4127 (3) | 0.4153 (2) | 0.6967 (2) | 0.0630 (11) | |
H33A | 0.4309 | 0.3951 | 0.6494 | 0.095* | |
H33B | 0.4702 | 0.4110 | 0.7277 | 0.095* | |
H33C | 0.3899 | 0.4789 | 0.6949 | 0.095* | |
C34 | 0.2333 (3) | 0.4989 (2) | 0.75890 (19) | 0.0583 (9) | |
H34A | 0.2762 | 0.5049 | 0.8000 | 0.087* | |
H34B | 0.1663 | 0.5185 | 0.7711 | 0.087* | |
H34C | 0.2586 | 0.5372 | 0.7207 | 0.087* | |
C35 | 0.2137 (4) | 0.0448 (3) | 0.8764 (3) | 0.0828 (14) | |
H35 | 0.1868 | 0.0568 | 0.9215 | 0.099* | |
C36 | 0.1602 (4) | 0.0152 (3) | 0.8174 (3) | 0.0752 (13) | |
H36 | 0.0914 | 0.0031 | 0.8161 | 0.090* | |
C37 | 0.2282 (4) | 0.0064 (2) | 0.7588 (2) | 0.0671 (10) | |
H37 | 0.2123 | −0.0114 | 0.7122 | 0.080* | |
C38 | 0.3244 (3) | 0.0299 (2) | 0.7853 (3) | 0.0722 (12) | |
H38 | 0.3836 | 0.0292 | 0.7586 | 0.087* | |
C39 | 0.3175 (4) | 0.0540 (3) | 0.8570 (3) | 0.0835 (14) | |
H39 | 0.3700 | 0.0726 | 0.8868 | 0.100* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ru | 0.04404 (13) | 0.03420 (11) | 0.04231 (13) | −0.00152 (11) | −0.00047 (12) | 0.00669 (12) |
P1 | 0.0351 (4) | 0.0374 (4) | 0.0371 (4) | 0.0005 (4) | −0.0021 (3) | 0.0008 (3) |
P2 | 0.0357 (4) | 0.0313 (3) | 0.0405 (4) | −0.0031 (3) | 0.0028 (4) | −0.0002 (4) |
Cl | 0.0789 (6) | 0.0613 (5) | 0.0382 (5) | −0.0063 (5) | 0.0087 (4) | −0.0042 (4) |
O | 0.0470 (13) | 0.0359 (11) | 0.0400 (12) | −0.0075 (10) | −0.0017 (10) | 0.0012 (9) |
N | 0.0327 (13) | 0.0362 (12) | 0.0553 (17) | −0.0039 (11) | −0.0036 (10) | 0.0082 (13) |
C1 | 0.0384 (18) | 0.0532 (19) | 0.050 (2) | 0.0054 (16) | 0.0008 (15) | −0.0029 (17) |
C2 | 0.054 (2) | 0.074 (2) | 0.061 (2) | 0.003 (2) | 0.0081 (17) | −0.028 (2) |
C3 | 0.088 (3) | 0.103 (4) | 0.078 (3) | 0.009 (3) | 0.009 (3) | −0.041 (3) |
C4 | 0.084 (3) | 0.135 (5) | 0.091 (4) | 0.003 (3) | 0.040 (3) | −0.045 (3) |
C5 | 0.068 (3) | 0.140 (5) | 0.103 (4) | −0.013 (3) | 0.037 (3) | −0.038 (4) |
C6 | 0.050 (2) | 0.096 (3) | 0.075 (3) | −0.008 (2) | 0.018 (2) | −0.018 (2) |
C7 | 0.0384 (17) | 0.0517 (19) | 0.0412 (19) | 0.0008 (16) | −0.0031 (13) | 0.0063 (15) |
C8 | 0.046 (2) | 0.067 (2) | 0.064 (2) | 0.0040 (18) | −0.0104 (18) | 0.0038 (19) |
C9 | 0.051 (2) | 0.095 (3) | 0.076 (3) | 0.008 (2) | −0.016 (2) | 0.022 (3) |
C10 | 0.060 (3) | 0.134 (4) | 0.052 (3) | 0.000 (3) | −0.020 (2) | 0.007 (3) |
C11 | 0.076 (3) | 0.118 (4) | 0.070 (3) | 0.003 (3) | −0.019 (2) | −0.028 (3) |
C12 | 0.054 (2) | 0.081 (3) | 0.059 (2) | 0.008 (2) | −0.0132 (18) | −0.011 (2) |
C13 | 0.0399 (15) | 0.0305 (13) | 0.0425 (16) | −0.0013 (14) | 0.0046 (14) | −0.0009 (12) |
C14 | 0.0369 (18) | 0.0303 (14) | 0.052 (2) | 0.0008 (13) | −0.0005 (14) | 0.0042 (14) |
C15 | 0.0465 (19) | 0.0397 (16) | 0.0444 (19) | −0.0077 (14) | −0.0115 (15) | 0.0096 (14) |
C16 | 0.058 (2) | 0.0600 (19) | 0.049 (2) | −0.0104 (19) | −0.0006 (18) | 0.0144 (16) |
C17 | 0.084 (3) | 0.088 (3) | 0.050 (2) | −0.023 (3) | 0.004 (2) | 0.011 (2) |
C18 | 0.106 (4) | 0.086 (3) | 0.061 (3) | −0.034 (3) | −0.018 (3) | 0.029 (2) |
C19 | 0.105 (4) | 0.053 (2) | 0.080 (3) | −0.022 (2) | −0.038 (3) | 0.031 (2) |
C20 | 0.071 (3) | 0.0451 (19) | 0.067 (3) | −0.0086 (19) | −0.028 (2) | 0.0124 (18) |
C21 | 0.0391 (18) | 0.0305 (15) | 0.069 (2) | −0.0030 (14) | 0.0075 (16) | −0.0042 (15) |
C22 | 0.050 (2) | 0.052 (2) | 0.083 (3) | 0.0025 (18) | −0.0043 (19) | 0.0019 (19) |
C23 | 0.044 (2) | 0.059 (2) | 0.121 (4) | 0.0018 (18) | −0.007 (2) | 0.003 (2) |
C24 | 0.047 (3) | 0.054 (2) | 0.135 (5) | 0.0059 (18) | 0.021 (3) | −0.001 (2) |
C25 | 0.067 (3) | 0.067 (2) | 0.094 (3) | −0.006 (2) | 0.033 (2) | −0.003 (2) |
C26 | 0.048 (2) | 0.052 (2) | 0.073 (3) | −0.0006 (16) | 0.0191 (19) | −0.0017 (19) |
C27 | 0.0362 (18) | 0.0409 (17) | 0.054 (2) | −0.0020 (14) | −0.0040 (15) | −0.0044 (15) |
C28 | 0.055 (2) | 0.048 (2) | 0.076 (3) | −0.0089 (17) | −0.0082 (19) | −0.0005 (19) |
C29 | 0.064 (3) | 0.051 (2) | 0.111 (4) | −0.014 (2) | −0.012 (3) | −0.021 (2) |
C30 | 0.102 (4) | 0.083 (3) | 0.093 (4) | −0.013 (3) | 0.000 (3) | −0.047 (3) |
C31 | 0.090 (3) | 0.106 (4) | 0.084 (3) | −0.031 (3) | 0.017 (3) | −0.052 (3) |
C32 | 0.063 (2) | 0.065 (2) | 0.056 (2) | −0.0117 (19) | 0.0045 (18) | −0.0172 (19) |
C33 | 0.046 (2) | 0.055 (2) | 0.089 (3) | −0.0103 (16) | 0.002 (2) | 0.019 (2) |
C34 | 0.075 (2) | 0.0404 (16) | 0.059 (2) | 0.0039 (19) | −0.007 (2) | −0.0078 (15) |
C35 | 0.124 (5) | 0.054 (2) | 0.070 (3) | −0.011 (3) | 0.007 (3) | 0.036 (2) |
C36 | 0.074 (3) | 0.044 (2) | 0.108 (4) | −0.007 (2) | −0.001 (3) | 0.026 (2) |
C37 | 0.077 (3) | 0.0311 (16) | 0.093 (3) | 0.001 (2) | −0.010 (3) | 0.0051 (17) |
C38 | 0.063 (3) | 0.0441 (19) | 0.110 (4) | 0.0105 (18) | −0.008 (3) | 0.018 (2) |
C39 | 0.087 (3) | 0.062 (3) | 0.101 (4) | −0.004 (2) | −0.031 (3) | 0.039 (3) |
Ru—C38 | 2.171 (4) | C16—H16 | 0.9300 |
Ru—C37 | 2.186 (3) | C17—C18 | 1.363 (6) |
Ru—C39 | 2.213 (4) | C17—H17 | 0.9300 |
Ru—C35 | 2.235 (4) | C18—C19 | 1.363 (6) |
Ru—C36 | 2.235 (4) | C18—H18 | 0.9300 |
Ru—P2 | 2.2675 (8) | C19—C20 | 1.414 (5) |
Ru—P1 | 2.2906 (8) | C19—H19 | 0.9300 |
Ru—Cl | 2.4382 (9) | C20—H20 | 0.9300 |
P1—N | 1.684 (2) | C21—C26 | 1.378 (5) |
P1—C1 | 1.838 (3) | C21—C22 | 1.391 (5) |
P1—C7 | 1.838 (3) | C22—C23 | 1.380 (5) |
P2—O | 1.631 (2) | C22—H22 | 0.9300 |
P2—C21 | 1.836 (3) | C23—C24 | 1.380 (6) |
P2—C27 | 1.837 (3) | C23—H23 | 0.9300 |
O—C14 | 1.445 (3) | C24—C25 | 1.361 (6) |
N—C33 | 1.457 (4) | C24—H24 | 0.9300 |
N—C13 | 1.471 (4) | C25—C26 | 1.403 (5) |
C1—C6 | 1.381 (5) | C25—H25 | 0.9300 |
C1—C2 | 1.394 (5) | C26—H26 | 0.9300 |
C2—C3 | 1.386 (5) | C27—C32 | 1.380 (5) |
C2—H2 | 0.9300 | C27—C28 | 1.393 (5) |
C3—C4 | 1.372 (6) | C28—C29 | 1.392 (5) |
C3—H3 | 0.9300 | C28—H28 | 0.9300 |
C4—C5 | 1.347 (7) | C29—C30 | 1.372 (6) |
C4—H4 | 0.9300 | C29—H29 | 0.9300 |
C5—C6 | 1.385 (5) | C30—C31 | 1.378 (6) |
C5—H5 | 0.9300 | C30—H30 | 0.9300 |
C6—H6 | 0.9300 | C31—C32 | 1.377 (5) |
C7—C8 | 1.385 (5) | C31—H31 | 0.9300 |
C7—C12 | 1.386 (5) | C32—H32 | 0.9300 |
C8—C9 | 1.389 (5) | C33—H33A | 0.9600 |
C8—H8 | 0.9300 | C33—H33B | 0.9600 |
C9—C10 | 1.356 (6) | C33—H33C | 0.9600 |
C9—H9 | 0.9300 | C34—H34A | 0.9600 |
C10—C11 | 1.388 (6) | C34—H34B | 0.9600 |
C10—H10 | 0.9300 | C34—H34C | 0.9600 |
C11—C12 | 1.382 (5) | C35—C36 | 1.377 (6) |
C11—H11 | 0.9300 | C35—C39 | 1.430 (6) |
C12—H12 | 0.9300 | C35—H35 | 0.9300 |
C13—C14 | 1.539 (4) | C36—C37 | 1.425 (6) |
C13—C34 | 1.540 (4) | C36—H36 | 0.9300 |
C13—H13 | 0.9800 | C37—C38 | 1.410 (5) |
C14—C15 | 1.508 (4) | C37—H37 | 0.9300 |
C14—H14 | 0.9800 | C38—C39 | 1.387 (6) |
C15—C16 | 1.376 (5) | C38—H38 | 0.9300 |
C15—C20 | 1.391 (4) | C39—H39 | 0.9300 |
C16—C17 | 1.393 (5) | ||
C38—Ru—C37 | 37.76 (15) | C20—C15—C14 | 119.8 (3) |
C38—Ru—C39 | 36.88 (17) | C15—C16—C17 | 121.5 (4) |
C37—Ru—C39 | 62.67 (17) | C15—C16—H16 | 119.2 |
C38—Ru—C35 | 61.65 (18) | C17—C16—H16 | 119.2 |
C37—Ru—C35 | 61.83 (17) | C18—C17—C16 | 119.6 (4) |
C39—Ru—C35 | 37.51 (16) | C18—C17—H17 | 120.2 |
C38—Ru—C36 | 62.05 (16) | C16—C17—H17 | 120.2 |
C37—Ru—C36 | 37.59 (15) | C17—C18—C19 | 120.7 (4) |
C39—Ru—C36 | 61.81 (16) | C17—C18—H18 | 119.7 |
C35—Ru—C36 | 35.90 (15) | C19—C18—H18 | 119.7 |
C38—Ru—P2 | 126.79 (14) | C18—C19—C20 | 120.1 (4) |
C37—Ru—P2 | 96.31 (12) | C18—C19—H19 | 120.0 |
C39—Ru—P2 | 158.67 (13) | C20—C19—H19 | 120.0 |
C35—Ru—P2 | 130.98 (15) | C15—C20—C19 | 119.6 (4) |
C36—Ru—P2 | 99.71 (12) | C15—C20—H20 | 120.2 |
C38—Ru—P1 | 91.46 (11) | C19—C20—H20 | 120.2 |
C37—Ru—P1 | 117.90 (13) | C26—C21—C22 | 118.4 (3) |
C39—Ru—P1 | 100.03 (13) | C26—C21—P2 | 121.9 (3) |
C35—Ru—P1 | 135.88 (15) | C22—C21—P2 | 119.6 (3) |
C36—Ru—P1 | 153.20 (13) | C23—C22—C21 | 121.3 (4) |
P2—Ru—P1 | 93.01 (3) | C23—C22—H22 | 119.3 |
C38—Ru—Cl | 135.41 (15) | C21—C22—H22 | 119.3 |
C37—Ru—Cl | 147.36 (12) | C22—C23—C24 | 119.5 (4) |
C39—Ru—Cl | 99.09 (16) | C22—C23—H23 | 120.2 |
C35—Ru—Cl | 87.00 (13) | C24—C23—H23 | 120.2 |
C36—Ru—Cl | 110.64 (14) | C25—C24—C23 | 120.2 (4) |
P2—Ru—Cl | 97.53 (3) | C25—C24—H24 | 119.9 |
P1—Ru—Cl | 90.73 (3) | C23—C24—H24 | 119.9 |
N—P1—C1 | 103.47 (14) | C24—C25—C26 | 120.3 (4) |
N—P1—C7 | 104.60 (14) | C24—C25—H25 | 119.8 |
C1—P1—C7 | 102.41 (15) | C26—C25—H25 | 119.8 |
N—P1—Ru | 119.63 (9) | C21—C26—C25 | 120.2 (4) |
C1—P1—Ru | 115.00 (12) | C21—C26—H26 | 119.9 |
C7—P1—Ru | 109.91 (10) | C25—C26—H26 | 119.9 |
O—P2—C21 | 102.49 (13) | C32—C27—C28 | 118.2 (3) |
O—P2—C27 | 95.05 (13) | C32—C27—P2 | 123.2 (3) |
C21—P2—C27 | 98.08 (14) | C28—C27—P2 | 118.6 (3) |
O—P2—Ru | 120.45 (8) | C29—C28—C27 | 120.6 (4) |
C21—P2—Ru | 120.29 (12) | C29—C28—H28 | 119.7 |
C27—P2—Ru | 115.60 (10) | C27—C28—H28 | 119.7 |
C14—O—P2 | 125.41 (19) | C30—C29—C28 | 119.7 (4) |
C33—N—C13 | 119.2 (2) | C30—C29—H29 | 120.2 |
C33—N—P1 | 120.0 (2) | C28—C29—H29 | 120.2 |
C13—N—P1 | 120.74 (18) | C29—C30—C31 | 120.3 (4) |
C6—C1—C2 | 117.4 (3) | C29—C30—H30 | 119.9 |
C6—C1—P1 | 124.5 (3) | C31—C30—H30 | 119.9 |
C2—C1—P1 | 118.0 (3) | C32—C31—C30 | 119.8 (4) |
C3—C2—C1 | 120.6 (4) | C32—C31—H31 | 120.1 |
C3—C2—H2 | 119.7 | C30—C31—H31 | 120.1 |
C1—C2—H2 | 119.7 | C31—C32—C27 | 121.4 (4) |
C4—C3—C2 | 120.3 (4) | C31—C32—H32 | 119.3 |
C4—C3—H3 | 119.8 | C27—C32—H32 | 119.3 |
C2—C3—H3 | 119.8 | N—C33—H33A | 109.5 |
C5—C4—C3 | 119.8 (4) | N—C33—H33B | 109.5 |
C5—C4—H4 | 120.1 | H33A—C33—H33B | 109.5 |
C3—C4—H4 | 120.1 | N—C33—H33C | 109.5 |
C4—C5—C6 | 120.6 (4) | H33A—C33—H33C | 109.5 |
C4—C5—H5 | 119.7 | H33B—C33—H33C | 109.5 |
C6—C5—H5 | 119.7 | C13—C34—H34A | 109.5 |
C1—C6—C5 | 121.3 (4) | C13—C34—H34B | 109.5 |
C1—C6—H6 | 119.3 | H34A—C34—H34B | 109.5 |
C5—C6—H6 | 119.3 | C13—C34—H34C | 109.5 |
C8—C7—C12 | 118.6 (3) | H34A—C34—H34C | 109.5 |
C8—C7—P1 | 121.5 (3) | H34B—C34—H34C | 109.5 |
C12—C7—P1 | 119.5 (3) | C36—C35—C39 | 108.9 (5) |
C7—C8—C9 | 121.0 (4) | C36—C35—Ru | 72.1 (2) |
C7—C8—H8 | 119.5 | C39—C35—Ru | 70.4 (2) |
C9—C8—H8 | 119.5 | C36—C35—H35 | 125.6 |
C10—C9—C8 | 120.3 (4) | C39—C35—H35 | 125.6 |
C10—C9—H9 | 119.9 | Ru—C35—H35 | 123.6 |
C8—C9—H9 | 119.9 | C35—C36—C37 | 108.3 (4) |
C9—C10—C11 | 119.3 (4) | C35—C36—Ru | 72.0 (2) |
C9—C10—H10 | 120.3 | C37—C36—Ru | 69.3 (2) |
C11—C10—H10 | 120.3 | C35—C36—H36 | 125.9 |
C12—C11—C10 | 121.0 (4) | C37—C36—H36 | 125.9 |
C12—C11—H11 | 119.5 | Ru—C36—H36 | 124.4 |
C10—C11—H11 | 119.5 | C38—C37—C36 | 106.5 (4) |
C11—C12—C7 | 119.7 (4) | C38—C37—Ru | 70.6 (2) |
C11—C12—H12 | 120.1 | C36—C37—Ru | 73.1 (2) |
C7—C12—H12 | 120.1 | C38—C37—H37 | 126.7 |
N—C13—C14 | 113.6 (2) | C36—C37—H37 | 126.7 |
N—C13—C34 | 113.2 (3) | Ru—C37—H37 | 121.4 |
C14—C13—C34 | 110.9 (2) | C39—C38—C37 | 109.7 (4) |
N—C13—H13 | 106.2 | C39—C38—Ru | 73.2 (2) |
C14—C13—H13 | 106.2 | C37—C38—Ru | 71.7 (2) |
C34—C13—H13 | 106.2 | C39—C38—H38 | 125.1 |
O—C14—C15 | 105.5 (2) | C37—C38—H38 | 125.1 |
O—C14—C13 | 111.0 (2) | Ru—C38—H38 | 121.6 |
C15—C14—C13 | 115.5 (2) | C38—C39—C35 | 106.6 (4) |
O—C14—H14 | 108.2 | C38—C39—Ru | 69.9 (2) |
C15—C14—H14 | 108.2 | C35—C39—Ru | 72.1 (2) |
C13—C14—H14 | 108.2 | C38—C39—H39 | 126.7 |
C16—C15—C20 | 118.5 (3) | C35—C39—H39 | 126.7 |
C16—C15—C14 | 121.7 (3) | Ru—C39—H39 | 123.0 |
Experimental details
Crystal data | |
Chemical formula | [Ru(C5H5)Cl(C34H33NOP2)] |
Mr | 735.16 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 296 |
a, b, c (Å) | 13.2734 (1), 14.3376 (1), 18.6640 (2) |
V (Å3) | 3551.92 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.64 |
Crystal size (mm) | 0.30 × 0.28 × 0.14 |
Data collection | |
Diffractometer | Make Model CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.832, 0.916 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 25398, 9351, 6619 |
Rint | 0.044 |
(sin θ/λ)max (Å−1) | 0.703 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.078, 1.01 |
No. of reflections | 9351 |
No. of parameters | 409 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.37, −0.59 |
Absolute structure | Flack (1983), with 3652 Friedel pairs Query |
Absolute structure parameter | −0.03 (2) |
Computer programs: SMART (Bruker, 2001), SMART, SHELXTL (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL.
Ru—P2 | 2.2675 (8) | P1—N | 1.684 (2) |
Ru—P1 | 2.2906 (8) | P2—O | 1.631 (2) |
Ru—Cl | 2.4382 (9) | ||
C38—Ru—P2 | 126.79 (14) | C38—Ru—Cl | 135.41 (15) |
C38—Ru—P1 | 91.46 (11) | P2—Ru—Cl | 97.53 (3) |
P2—Ru—P1 | 93.01 (3) | P1—Ru—Cl | 90.73 (3) |
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Organometallic complexes containing a chiral metal centre have attracted considerable attention, due to their potential application as reagents in asymmetric synthesis (Brunner, 1999). For this purpose, half-sandwich Cp—Ru complexes bearing a chelating diphosphine without C2v symmetry are attractive targets, since these species have been shown to be configurationally stable at the chiral metal centre (Davies et al., 1990). Here, we present the molecular structure of the title complex, (I), a new optically pure half-sandwich Ru complex, which was obtained by reaction of the diphosphine (+)-(2S,3R)-2-[(diphenylphosphino)methylamino]-3-phenylpropyl diphenylphosphinite with ClRuCpPPh3. \sch
Compound (I) was synthesized as a single diastereomer and crystallized from a pentane-CH2Cl2 solvent mixture in the chiral space group P212121. Our X-ray data allowed determination of the absolute configuration at the Ru centre in (I). The molecular structure of (I) is shown in Fig. 1 and selected dimensions are given in Table 1.
The Ru atom in complex (I) adopts a pseudo-octahedral coordination geometry, which can also be described as a distorted tetrahedral structure if one simplifies the Ru(η5-C5H5) moiety to an Ru—Cg (Cg is the Cp centroid) moiety. The P1—Ru—P2, P1—Ru—Cl and P2—Ru—Cl bond angles [mean 93.76 (3)°] are smaller than the ideal tetrahedral angle (109.47°), which is compensated for by the opening of the Cp—Ru—L L is what? angles [122.44 (15)°]. In accordance with the stereochemical convention adopted for organometallics (Brunner et al., 1980), the ligand priority is C5H5 〉 Cl 〉 P(O) 〉 P(N) and the absolute configuration of the metal centre is S. The seven-membered Ru-ligand chelate ring adopts a boat-like conformation, with the O atom being very close to the Ru—P1—P2 plane, as shown by the small O—P1—Ru—P2 torsion angle (-5.0°). The N atom is clearly out of the Ru—P1—P2 plane (P2—Ru—P1—N 42.6°).
The Ru—P(N) and Ru—P(O) bond distances [2.2906 (8) and 2.2675 (8) Å, respectively] are slightly longer than those in the related complex (S)—Ru(η5-C5H5)[(S)-dpompyr-PP']Cl [2.269 (2) and 2.242 Å, respectively; dpompyr-PP' is?; Cesarotti et al., 1987]. The Ru—P(N) distance is longer than the Ru—P(O) distance, as is generally observed in transition metal complexes containing aminophosphine-phosphinite ligands (Cesarotti et al., 1987, 1992).