metal-organic compounds
[(R)-2,2-Bis(diphenylphosphanyl)-1,1′-binaphthyl-κ2P,P′]{2-[(2R)-1,2-diamino-1-(4-methoxyphenyl)-3-methylbutyl]-5-methoxyphenyl-κC1}hydridoruthenium(II) benzene monosolvate
aKanata Chemical Technologies Inc., 101 College Street, Office 230, Toronto, Ontario, Canada M5G 1L7, and bDepartment of Chemistry, University of Toronto, Toronto, Ontario, Canada M5S 3H6
*Correspondence e-mail: alough@chem.utoronto.ca
In the title complex, [Ru(C19H25N2O2)H(C44H32P2)]·C6H6, the RuII ion is in a distorted octahedral coordination environment with the hydride H atom trans to the tertiary carbinamine N atom, giving an H—Ru—N angle of 160.8 (12)°. The equatorial sites are occupied by two P atoms, the secondary carbinamine N atom and a coordinated C atom.
Related literature
For the synthesis of Ru(II) hydride complexes with an RuN2P2 coordination environment, see: Abdur-Rashid, Faatz et al. (2001); Abdur-Rashid, Abbel et al. (2005); Ohkuma et al. (1995). For their use as catalysts, see: Abdur-Rashid, Guo et al. (2005); Abdur-Rashid et al. (2000); Abdur-Rashid, Lough et al. (2001); Cobley & Henschke (2003); Doucet et al. (1998); Matsumura et al. (2011). For related structures, see: Guo et al. (2004); Li et al. (2004). For kinetic studies, see: Abbel et al. (2005); Abdur-Rashid et al. (2002).
Experimental
Crystal data
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Data collection: COLLECT (Nonius, 2002); cell DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536812046065/vm2180sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812046065/vm2180Isup2.hkl
A solution of K-Selectride (100 ml of a 1.0 M solution in THF) was added to a solution of RuHCl(R-binap)(R-daipen) (100 mg) in THF (5 ml) and the mixture stirred under hydrogen gas at room temperature for 2 h. The mixture was filtered and the filtrate evaporated to dryness to give the bright yellow dihydride compound RuH2(R-binap)(R-daipen) (1) [R-Binap = (R)-bis(diphenylphosphanyl)-1,1-binaphthyl and R-Daipen = (R)-1,1-Bis(4-methoxyphenyl)-3-methylbutane-1,2-diamine]. This was suspended in hexanes (5 ml) and the suspension stirred for 48 h at room temperature under argon. The solids were filtered and washed with hexanes (5 ml) and dried under vacuum to give 76 mg of the hydridoruthenabicyclic compound (I) as a bright yellow solid. X-ray diffraction quality single crystals were grown by the slow diffusion of hexanes into a solution of (I) in benzene.
Hydrogen atoms bonded to C atoms were placed in calculated positions with C—H = 0.95–1.00 Å and were included in the
in a riding-model approximation with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C) for methyl C atoms. The hydride and amine H atoms were refined independently with isotropic displacement parameters. The benzene solvent molecule was fitted as a regular hexagon with C—C = 1.39 Å using the AFIX 66 command in SHELXL (Sheldrick, 2008).Data collection: COLLECT (Nonius, 2002); cell
DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).[Ru(C19H25N2O2)H(C44H32P2)]·C6H6 | F(000) = 2328 |
Mr = 1116.23 | Dx = 1.330 Mg m−3 |
Monoclinic, C2 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C 2y | Cell parameters from 11534 reflections |
a = 38.8848 (8) Å | θ = 2.7–27.5° |
b = 13.5741 (3) Å | µ = 0.39 mm−1 |
c = 10.8871 (2) Å | T = 150 K |
β = 103.967 (1)° | Block, yellow |
V = 5576.6 (2) Å3 | 0.35 × 0.32 × 0.25 mm |
Z = 4 |
Nonius KappaCCD diffractometer | 11534 independent reflections |
Radiation source: fine-focus sealed tube | 10079 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.051 |
Detector resolution: 9 pixels mm-1 | θmax = 27.5°, θmin = 2.7° |
ϕ scans and ω scans with κ offsets | h = −50→50 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | k = −17→17 |
Tmin = 0.876, Tmax = 0.909 | l = −14→14 |
21246 measured reflections |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.039 | w = 1/[σ2(Fo2) + (0.0286P)2 + 2.2793P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.089 | (Δ/σ)max = 0.002 |
S = 1.04 | Δρmax = 0.54 e Å−3 |
11534 reflections | Δρmin = −0.54 e Å−3 |
698 parameters | Extinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1 restraint | Extinction coefficient: 0.00045 (11) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), 4924 Friedel pairs |
Secondary atom site location: difference Fourier map | Absolute structure parameter: −0.045 (19) |
[Ru(C19H25N2O2)H(C44H32P2)]·C6H6 | V = 5576.6 (2) Å3 |
Mr = 1116.23 | Z = 4 |
Monoclinic, C2 | Mo Kα radiation |
a = 38.8848 (8) Å | µ = 0.39 mm−1 |
b = 13.5741 (3) Å | T = 150 K |
c = 10.8871 (2) Å | 0.35 × 0.32 × 0.25 mm |
β = 103.967 (1)° |
Nonius KappaCCD diffractometer | 11534 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 10079 reflections with I > 2σ(I) |
Tmin = 0.876, Tmax = 0.909 | Rint = 0.051 |
21246 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.089 | Δρmax = 0.54 e Å−3 |
S = 1.04 | Δρmin = −0.54 e Å−3 |
11534 reflections | Absolute structure: Flack (1983), 4924 Friedel pairs |
698 parameters | Absolute structure parameter: −0.045 (19) |
1 restraint |
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 | ||
Ru1 | 0.365924 (6) | 0.782933 (18) | 0.603130 (19) | 0.02226 (7) | |
H1RU | 0.3380 (8) | 0.809 (3) | 0.685 (3) | 0.029 (9)* | |
P1 | 0.40933 (2) | 0.81338 (6) | 0.77366 (7) | 0.02362 (18) | |
P2 | 0.35821 (2) | 0.94374 (6) | 0.54146 (7) | 0.02201 (17) | |
O1 | 0.33911 (8) | 0.4662 (2) | 0.8879 (2) | 0.0368 (7) | |
O2 | 0.44751 (7) | 0.3603 (2) | 0.1801 (2) | 0.0398 (6) | |
N1 | 0.32414 (7) | 0.7297 (2) | 0.4435 (3) | 0.0275 (6) | |
H1B | 0.3095 (10) | 0.778 (4) | 0.392 (4) | 0.056 (11)* | |
H1C | 0.3104 (12) | 0.705 (3) | 0.489 (4) | 0.048 (13)* | |
N2 | 0.39494 (7) | 0.6998 (2) | 0.4842 (3) | 0.0247 (6) | |
H2A | 0.4178 (11) | 0.684 (3) | 0.534 (3) | 0.039 (11)* | |
H2B | 0.3993 (9) | 0.725 (3) | 0.428 (3) | 0.016 (9)* | |
C1 | 0.33628 (8) | 0.6555 (2) | 0.3619 (3) | 0.0254 (7) | |
H1A | 0.3421 | 0.6927 | 0.2903 | 0.031* | |
C2 | 0.37185 (8) | 0.6111 (2) | 0.4411 (3) | 0.0236 (6) | |
C3 | 0.30748 (10) | 0.5792 (3) | 0.3020 (3) | 0.0317 (8) | |
H3A | 0.3198 | 0.5172 | 0.2871 | 0.038* | |
C4 | 0.28619 (11) | 0.6170 (4) | 0.1732 (4) | 0.0482 (11) | |
H4A | 0.2681 | 0.5684 | 0.1354 | 0.072* | |
H4B | 0.3022 | 0.6272 | 0.1172 | 0.072* | |
H4C | 0.2747 | 0.6794 | 0.1848 | 0.072* | |
C5 | 0.28160 (9) | 0.5531 (3) | 0.3852 (3) | 0.0368 (8) | |
H5A | 0.2951 | 0.5361 | 0.4707 | 0.055* | |
H5B | 0.2669 | 0.4969 | 0.3481 | 0.055* | |
H5C | 0.2664 | 0.6099 | 0.3894 | 0.055* | |
C6 | 0.36574 (8) | 0.5661 (3) | 0.5624 (3) | 0.0260 (7) | |
C7 | 0.36063 (8) | 0.4660 (3) | 0.5759 (3) | 0.0279 (7) | |
H7A | 0.3635 | 0.4223 | 0.5109 | 0.033* | |
C8 | 0.35141 (9) | 0.4281 (3) | 0.6828 (3) | 0.0315 (7) | |
H8A | 0.3475 | 0.3595 | 0.6909 | 0.038* | |
C9 | 0.34817 (9) | 0.4944 (3) | 0.7772 (3) | 0.0294 (7) | |
C10 | 0.35333 (9) | 0.5946 (2) | 0.7629 (3) | 0.0279 (7) | |
H10A | 0.3507 | 0.6378 | 0.8288 | 0.033* | |
C11 | 0.36215 (8) | 0.6352 (2) | 0.6568 (3) | 0.0237 (6) | |
C12 | 0.33415 (11) | 0.3639 (3) | 0.9057 (4) | 0.0443 (10) | |
H12A | 0.3284 | 0.3535 | 0.9876 | 0.066* | |
H12B | 0.3559 | 0.3282 | 0.9039 | 0.066* | |
H12C | 0.3147 | 0.3394 | 0.8378 | 0.066* | |
C13 | 0.39027 (8) | 0.5435 (2) | 0.3657 (3) | 0.0266 (7) | |
C14 | 0.38130 (9) | 0.5383 (3) | 0.2346 (3) | 0.0315 (8) | |
H14A | 0.3621 | 0.5770 | 0.1888 | 0.038* | |
C15 | 0.39949 (9) | 0.4781 (3) | 0.1678 (3) | 0.0325 (8) | |
H15A | 0.3926 | 0.4755 | 0.0780 | 0.039* | |
C16 | 0.42779 (9) | 0.4219 (3) | 0.2338 (3) | 0.0320 (7) | |
C17 | 0.43839 (9) | 0.4296 (3) | 0.3658 (3) | 0.0320 (8) | |
H17A | 0.4584 | 0.3936 | 0.4113 | 0.038* | |
C18 | 0.41996 (9) | 0.4893 (3) | 0.4300 (3) | 0.0308 (7) | |
H18A | 0.4275 | 0.4939 | 0.5196 | 0.037* | |
C19 | 0.43718 (12) | 0.3472 (3) | 0.0455 (4) | 0.0470 (10) | |
H19A | 0.4545 | 0.3050 | 0.0188 | 0.071* | |
H19B | 0.4363 | 0.4114 | 0.0038 | 0.071* | |
H19C | 0.4137 | 0.3163 | 0.0221 | 0.071* | |
C20 | 0.37929 (8) | 1.0340 (2) | 0.7784 (3) | 0.0242 (6) | |
C21 | 0.35121 (8) | 1.0207 (2) | 0.6733 (3) | 0.0249 (7) | |
C22 | 0.31719 (8) | 1.0571 (3) | 0.6782 (3) | 0.0287 (7) | |
H22A | 0.2982 | 1.0527 | 0.6048 | 0.034* | |
C23 | 0.31115 (9) | 1.0981 (3) | 0.7854 (3) | 0.0328 (8) | |
H23A | 0.2882 | 1.1226 | 0.7848 | 0.039* | |
C24 | 0.33835 (10) | 1.1045 (3) | 0.8968 (3) | 0.0298 (8) | |
C25 | 0.33263 (10) | 1.1434 (3) | 1.0118 (3) | 0.0346 (8) | |
H25A | 0.3095 | 1.1645 | 1.0145 | 0.042* | |
C26 | 0.35911 (11) | 1.1509 (3) | 1.1161 (3) | 0.0403 (9) | |
H26A | 0.3548 | 1.1785 | 1.1912 | 0.048* | |
C27 | 0.39342 (11) | 1.1178 (3) | 1.1146 (3) | 0.0414 (9) | |
H27A | 0.4119 | 1.1215 | 1.1895 | 0.050* | |
C28 | 0.40020 (10) | 1.0803 (3) | 1.0063 (3) | 0.0322 (8) | |
H28A | 0.4235 | 1.0592 | 1.0065 | 0.039* | |
C29 | 0.37304 (9) | 1.0725 (2) | 0.8940 (3) | 0.0270 (7) | |
C30 | 0.41747 (8) | 1.0206 (2) | 0.7768 (3) | 0.0227 (6) | |
C31 | 0.43490 (8) | 0.9308 (3) | 0.7890 (3) | 0.0250 (7) | |
C32 | 0.47271 (9) | 0.9318 (3) | 0.8113 (3) | 0.0300 (7) | |
H32A | 0.4853 | 0.8714 | 0.8274 | 0.036* | |
C33 | 0.49113 (9) | 1.0167 (3) | 0.8102 (3) | 0.0306 (8) | |
H33A | 0.5162 | 1.0143 | 0.8253 | 0.037* | |
C34 | 0.47370 (8) | 1.1086 (3) | 0.7871 (3) | 0.0275 (7) | |
C35 | 0.49190 (9) | 1.1972 (3) | 0.7781 (3) | 0.0342 (8) | |
H35A | 0.5168 | 1.1957 | 0.7875 | 0.041* | |
C36 | 0.47426 (8) | 1.2858 (4) | 0.7560 (3) | 0.0349 (7) | |
H36A | 0.4868 | 1.3447 | 0.7487 | 0.042* | |
C37 | 0.43762 (8) | 1.2884 (3) | 0.7444 (3) | 0.0327 (7) | |
H37A | 0.4254 | 1.3495 | 0.7301 | 0.039* | |
C38 | 0.41919 (9) | 1.2040 (2) | 0.7533 (3) | 0.0272 (7) | |
H38A | 0.3944 | 1.2077 | 0.7459 | 0.033* | |
C39 | 0.43620 (8) | 1.1113 (2) | 0.7731 (3) | 0.0250 (7) | |
C41 | 0.31730 (8) | 0.9610 (2) | 0.4156 (3) | 0.0256 (7) | |
C42 | 0.28469 (9) | 0.9283 (3) | 0.4369 (3) | 0.0295 (7) | |
H42A | 0.2840 | 0.9022 | 0.5172 | 0.035* | |
C43 | 0.25372 (9) | 0.9338 (3) | 0.3420 (3) | 0.0384 (8) | |
H43A | 0.2318 | 0.9140 | 0.3585 | 0.046* | |
C44 | 0.25466 (10) | 0.9684 (3) | 0.2222 (4) | 0.0493 (11) | |
H44A | 0.2335 | 0.9732 | 0.1572 | 0.059* | |
C45 | 0.28661 (11) | 0.9954 (4) | 0.1995 (4) | 0.0485 (11) | |
H45A | 0.2876 | 1.0158 | 0.1169 | 0.058* | |
C46 | 0.31755 (10) | 0.9933 (3) | 0.2953 (3) | 0.0347 (9) | |
H46A | 0.3392 | 1.0144 | 0.2779 | 0.042* | |
C51 | 0.39023 (8) | 1.0214 (3) | 0.4854 (3) | 0.0270 (7) | |
C52 | 0.42172 (9) | 0.9793 (3) | 0.4729 (3) | 0.0354 (8) | |
H52A | 0.4252 | 0.9102 | 0.4825 | 0.042* | |
C53 | 0.44850 (10) | 1.0390 (4) | 0.4461 (3) | 0.0517 (12) | |
H53A | 0.4700 | 1.0101 | 0.4371 | 0.062* | |
C54 | 0.44376 (12) | 1.1387 (4) | 0.4328 (4) | 0.0570 (14) | |
H54A | 0.4623 | 1.1787 | 0.4168 | 0.068* | |
C55 | 0.41235 (13) | 1.1818 (3) | 0.4424 (3) | 0.0487 (11) | |
H55A | 0.4089 | 1.2508 | 0.4311 | 0.058* | |
C56 | 0.38568 (10) | 1.1226 (3) | 0.4688 (3) | 0.0348 (8) | |
H56A | 0.3640 | 1.1520 | 0.4756 | 0.042* | |
C61 | 0.44425 (9) | 0.7199 (3) | 0.7828 (3) | 0.0303 (7) | |
C62 | 0.46595 (9) | 0.7245 (3) | 0.6967 (3) | 0.0332 (8) | |
H62A | 0.4641 | 0.7800 | 0.6424 | 0.040* | |
C63 | 0.48997 (10) | 0.6504 (3) | 0.6887 (4) | 0.0408 (9) | |
H63A | 0.5047 | 0.6554 | 0.6308 | 0.049* | |
C64 | 0.49206 (12) | 0.5694 (3) | 0.7665 (5) | 0.0534 (12) | |
H64A | 0.5086 | 0.5185 | 0.7634 | 0.064* | |
C65 | 0.47035 (12) | 0.5619 (3) | 0.8486 (4) | 0.0543 (11) | |
H65A | 0.4714 | 0.5046 | 0.8995 | 0.065* | |
C66 | 0.44688 (10) | 0.6369 (3) | 0.8581 (4) | 0.0406 (9) | |
H66A | 0.4325 | 0.6312 | 0.9170 | 0.049* | |
C71 | 0.40170 (9) | 0.8134 (2) | 0.9349 (3) | 0.0298 (7) | |
C72 | 0.36758 (9) | 0.8250 (3) | 0.9506 (3) | 0.0327 (7) | |
H72A | 0.3480 | 0.8238 | 0.8788 | 0.039* | |
C73 | 0.36170 (11) | 0.8386 (3) | 1.0712 (3) | 0.0396 (9) | |
H73A | 0.3382 | 0.8465 | 1.0806 | 0.048* | |
C74 | 0.38965 (12) | 0.8404 (3) | 1.1762 (3) | 0.0429 (10) | |
H74A | 0.3856 | 0.8518 | 1.2576 | 0.052* | |
C75 | 0.42389 (12) | 0.8256 (3) | 1.1626 (3) | 0.0474 (10) | |
H75A | 0.4431 | 0.8239 | 1.2354 | 0.057* | |
C76 | 0.43013 (10) | 0.8134 (3) | 1.0431 (3) | 0.0386 (9) | |
H76A | 0.4537 | 0.8049 | 1.0344 | 0.046* | |
C1S | 0.23578 (10) | 0.2324 (4) | 0.2839 (5) | 0.113 (3) | |
H1SA | 0.2148 | 0.2043 | 0.2993 | 0.135* | |
C2S | 0.23558 (14) | 0.2706 (5) | 0.1653 (4) | 0.141 (4) | |
H2SA | 0.2145 | 0.2686 | 0.0996 | 0.170* | |
C3S | 0.2662 (2) | 0.3117 (4) | 0.1429 (4) | 0.134 (4) | |
H3SA | 0.2661 | 0.3378 | 0.0619 | 0.160* | |
C4S | 0.29709 (15) | 0.3146 (3) | 0.2392 (7) | 0.119 (3) | |
H4SA | 0.3180 | 0.3427 | 0.2239 | 0.143* | |
C5S | 0.29729 (9) | 0.2764 (4) | 0.3578 (5) | 0.101 (2) | |
H5SA | 0.3184 | 0.2784 | 0.4236 | 0.122* | |
C6S | 0.26664 (14) | 0.2353 (3) | 0.3802 (4) | 0.0886 (18) | |
H6SA | 0.2668 | 0.2092 | 0.4613 | 0.106* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ru1 | 0.01979 (11) | 0.02082 (11) | 0.02517 (11) | −0.00075 (12) | 0.00348 (8) | −0.00106 (12) |
P1 | 0.0211 (4) | 0.0227 (4) | 0.0256 (4) | 0.0000 (3) | 0.0029 (3) | −0.0001 (3) |
P2 | 0.0188 (4) | 0.0225 (4) | 0.0243 (4) | −0.0010 (3) | 0.0042 (3) | −0.0011 (3) |
O1 | 0.0467 (17) | 0.0315 (16) | 0.0327 (14) | −0.0044 (13) | 0.0104 (12) | 0.0072 (12) |
O2 | 0.0353 (14) | 0.0433 (15) | 0.0419 (14) | 0.0072 (12) | 0.0116 (12) | −0.0109 (11) |
N1 | 0.0214 (14) | 0.0269 (16) | 0.0313 (14) | 0.0012 (12) | 0.0005 (12) | −0.0045 (12) |
N2 | 0.0241 (15) | 0.0223 (15) | 0.0274 (14) | −0.0010 (12) | 0.0057 (12) | 0.0008 (12) |
C1 | 0.0222 (15) | 0.0253 (17) | 0.0267 (15) | 0.0007 (13) | 0.0018 (12) | −0.0021 (13) |
C2 | 0.0245 (16) | 0.0203 (16) | 0.0246 (15) | −0.0034 (13) | 0.0029 (12) | −0.0023 (12) |
C3 | 0.0270 (19) | 0.0313 (19) | 0.0344 (18) | −0.0028 (16) | 0.0027 (14) | −0.0073 (15) |
C4 | 0.034 (2) | 0.072 (3) | 0.034 (2) | −0.008 (2) | −0.0001 (16) | −0.008 (2) |
C5 | 0.0269 (18) | 0.038 (2) | 0.0444 (19) | −0.0074 (16) | 0.0065 (15) | −0.0074 (16) |
C6 | 0.0210 (16) | 0.0236 (17) | 0.0317 (16) | −0.0005 (14) | 0.0028 (13) | 0.0007 (14) |
C7 | 0.0231 (16) | 0.0248 (17) | 0.0351 (17) | 0.0013 (14) | 0.0060 (13) | −0.0031 (14) |
C8 | 0.0289 (18) | 0.0214 (17) | 0.0419 (18) | −0.0012 (14) | 0.0039 (14) | 0.0054 (15) |
C9 | 0.0239 (17) | 0.0295 (18) | 0.0330 (17) | 0.0019 (14) | 0.0031 (13) | 0.0090 (14) |
C10 | 0.0274 (17) | 0.0253 (18) | 0.0288 (16) | −0.0030 (14) | 0.0029 (13) | 0.0022 (13) |
C11 | 0.0204 (15) | 0.0226 (16) | 0.0269 (15) | −0.0017 (13) | 0.0031 (12) | 0.0026 (13) |
C12 | 0.049 (2) | 0.034 (2) | 0.052 (2) | −0.0016 (19) | 0.017 (2) | 0.0153 (18) |
C13 | 0.0233 (16) | 0.0259 (17) | 0.0305 (16) | 0.0002 (14) | 0.0059 (12) | −0.0012 (13) |
C14 | 0.0284 (18) | 0.036 (2) | 0.0293 (16) | 0.0030 (15) | 0.0051 (13) | −0.0003 (15) |
C15 | 0.0311 (19) | 0.034 (2) | 0.0316 (18) | −0.0008 (16) | 0.0060 (15) | −0.0009 (15) |
C16 | 0.0301 (18) | 0.0269 (18) | 0.0417 (18) | −0.0060 (15) | 0.0137 (15) | −0.0072 (15) |
C17 | 0.0264 (18) | 0.033 (2) | 0.0357 (18) | 0.0039 (16) | 0.0048 (14) | 0.0006 (16) |
C18 | 0.0291 (18) | 0.0301 (18) | 0.0307 (17) | 0.0012 (15) | 0.0025 (14) | −0.0027 (14) |
C19 | 0.052 (2) | 0.050 (3) | 0.043 (2) | 0.008 (2) | 0.0173 (19) | −0.0104 (19) |
C20 | 0.0245 (16) | 0.0206 (16) | 0.0281 (15) | 0.0001 (13) | 0.0077 (12) | −0.0001 (13) |
C21 | 0.0231 (16) | 0.0236 (17) | 0.0284 (15) | 0.0008 (14) | 0.0067 (12) | 0.0020 (13) |
C22 | 0.0197 (16) | 0.0310 (19) | 0.0350 (17) | 0.0024 (14) | 0.0057 (13) | −0.0044 (14) |
C23 | 0.0244 (17) | 0.034 (2) | 0.0435 (19) | 0.0001 (15) | 0.0141 (15) | −0.0099 (16) |
C24 | 0.033 (2) | 0.026 (2) | 0.0345 (19) | −0.0032 (16) | 0.0158 (16) | −0.0049 (15) |
C25 | 0.038 (2) | 0.030 (2) | 0.042 (2) | 0.0004 (16) | 0.0214 (16) | −0.0015 (16) |
C26 | 0.063 (3) | 0.032 (2) | 0.0300 (18) | 0.0003 (18) | 0.0198 (17) | −0.0032 (15) |
C27 | 0.051 (2) | 0.043 (2) | 0.0293 (18) | 0.001 (2) | 0.0080 (17) | −0.0016 (17) |
C28 | 0.0345 (19) | 0.0322 (19) | 0.0303 (16) | 0.0040 (16) | 0.0082 (14) | −0.0018 (14) |
C29 | 0.0328 (18) | 0.0225 (16) | 0.0274 (15) | −0.0036 (14) | 0.0102 (13) | 0.0001 (13) |
C30 | 0.0215 (15) | 0.0239 (16) | 0.0223 (14) | −0.0029 (13) | 0.0047 (11) | −0.0049 (12) |
C31 | 0.0231 (16) | 0.0268 (18) | 0.0250 (15) | −0.0019 (14) | 0.0055 (12) | 0.0014 (13) |
C32 | 0.0231 (16) | 0.0271 (18) | 0.0384 (17) | 0.0051 (14) | 0.0046 (13) | −0.0030 (14) |
C33 | 0.0170 (16) | 0.0304 (19) | 0.0440 (19) | −0.0010 (14) | 0.0066 (14) | −0.0070 (16) |
C34 | 0.0240 (16) | 0.0285 (18) | 0.0309 (16) | −0.0037 (14) | 0.0081 (13) | −0.0062 (13) |
C35 | 0.0257 (17) | 0.034 (2) | 0.0443 (19) | −0.0078 (15) | 0.0114 (15) | −0.0054 (16) |
C36 | 0.0359 (16) | 0.0251 (15) | 0.0465 (16) | −0.006 (2) | 0.0157 (13) | −0.003 (2) |
C37 | 0.0356 (16) | 0.0276 (17) | 0.0356 (14) | 0.001 (2) | 0.0096 (12) | −0.0017 (19) |
C38 | 0.0261 (17) | 0.0268 (18) | 0.0278 (15) | −0.0022 (14) | 0.0050 (13) | −0.0022 (13) |
C39 | 0.0247 (16) | 0.0262 (17) | 0.0241 (15) | −0.0033 (14) | 0.0061 (12) | −0.0070 (13) |
C41 | 0.0217 (16) | 0.0221 (16) | 0.0323 (16) | −0.0023 (13) | 0.0053 (13) | −0.0041 (13) |
C42 | 0.0265 (17) | 0.0284 (18) | 0.0319 (16) | −0.0002 (15) | 0.0036 (13) | −0.0019 (14) |
C43 | 0.0257 (18) | 0.040 (2) | 0.046 (2) | 0.0023 (17) | 0.0025 (15) | 0.0000 (17) |
C44 | 0.031 (2) | 0.063 (3) | 0.044 (2) | −0.010 (2) | −0.0103 (16) | 0.009 (2) |
C45 | 0.038 (2) | 0.068 (3) | 0.033 (2) | −0.013 (2) | −0.0042 (16) | 0.011 (2) |
C46 | 0.0270 (19) | 0.043 (2) | 0.0316 (18) | −0.0062 (17) | 0.0020 (15) | 0.0018 (16) |
C51 | 0.0241 (16) | 0.0345 (19) | 0.0206 (14) | −0.0043 (15) | 0.0018 (12) | −0.0033 (13) |
C52 | 0.0264 (18) | 0.053 (2) | 0.0267 (16) | −0.0031 (16) | 0.0074 (13) | −0.0045 (15) |
C53 | 0.029 (2) | 0.097 (4) | 0.0314 (19) | −0.015 (2) | 0.0104 (15) | −0.008 (2) |
C54 | 0.050 (3) | 0.090 (4) | 0.031 (2) | −0.050 (3) | 0.0090 (18) | −0.005 (2) |
C55 | 0.071 (3) | 0.046 (2) | 0.0299 (18) | −0.032 (2) | 0.0137 (18) | −0.0001 (17) |
C56 | 0.043 (2) | 0.036 (2) | 0.0254 (16) | −0.0092 (18) | 0.0075 (15) | −0.0007 (15) |
C61 | 0.0243 (17) | 0.0277 (18) | 0.0347 (17) | 0.0008 (14) | −0.0011 (13) | −0.0042 (14) |
C62 | 0.0271 (18) | 0.033 (2) | 0.0359 (18) | 0.0049 (15) | 0.0010 (14) | −0.0093 (15) |
C63 | 0.0277 (18) | 0.037 (2) | 0.056 (2) | 0.0038 (16) | 0.0061 (16) | −0.0146 (18) |
C64 | 0.034 (2) | 0.041 (3) | 0.083 (3) | 0.008 (2) | 0.009 (2) | −0.007 (2) |
C65 | 0.047 (3) | 0.033 (2) | 0.079 (3) | 0.009 (2) | 0.007 (2) | 0.011 (2) |
C66 | 0.033 (2) | 0.032 (2) | 0.054 (2) | −0.0013 (17) | 0.0036 (17) | 0.0073 (18) |
C71 | 0.0344 (17) | 0.0259 (18) | 0.0279 (15) | −0.0046 (14) | 0.0053 (13) | 0.0002 (12) |
C72 | 0.0350 (19) | 0.0342 (18) | 0.0291 (16) | −0.0041 (15) | 0.0084 (14) | −0.0033 (14) |
C73 | 0.042 (2) | 0.044 (2) | 0.0365 (18) | −0.0026 (18) | 0.0168 (16) | −0.0014 (17) |
C74 | 0.063 (3) | 0.041 (2) | 0.0257 (18) | −0.007 (2) | 0.0133 (17) | 0.0020 (16) |
C75 | 0.057 (3) | 0.053 (2) | 0.0252 (17) | −0.008 (2) | −0.0026 (16) | 0.0030 (16) |
C76 | 0.0342 (18) | 0.046 (2) | 0.0329 (16) | −0.0025 (16) | 0.0026 (14) | 0.0028 (15) |
C1S | 0.059 (4) | 0.151 (7) | 0.138 (6) | −0.013 (4) | 0.044 (4) | −0.062 (5) |
C2S | 0.104 (6) | 0.227 (11) | 0.082 (4) | 0.089 (7) | 0.000 (4) | −0.020 (6) |
C3S | 0.199 (9) | 0.117 (8) | 0.111 (6) | 0.067 (7) | 0.090 (7) | 0.006 (5) |
C4S | 0.128 (7) | 0.055 (4) | 0.215 (9) | −0.013 (4) | 0.120 (7) | −0.041 (5) |
C5S | 0.063 (3) | 0.070 (4) | 0.158 (6) | 0.010 (4) | 0.000 (4) | −0.055 (5) |
C6S | 0.110 (5) | 0.067 (4) | 0.088 (4) | 0.010 (4) | 0.024 (4) | 0.005 (3) |
Ru1—H1RU | 1.60 (3) | C27—H27A | 0.9500 |
Ru1—C11 | 2.104 (3) | C28—C29 | 1.413 (5) |
Ru1—N1 | 2.195 (3) | C28—H28A | 0.9500 |
Ru1—N2 | 2.219 (3) | C30—C31 | 1.386 (5) |
Ru1—P1 | 2.2258 (8) | C30—C39 | 1.435 (5) |
Ru1—P2 | 2.2821 (9) | C31—C32 | 1.431 (4) |
P1—C61 | 1.843 (3) | C32—C33 | 1.358 (5) |
P1—C71 | 1.849 (3) | C32—H32A | 0.9500 |
P1—C31 | 1.864 (3) | C33—C34 | 1.412 (5) |
P2—C51 | 1.845 (3) | C33—H33A | 0.9500 |
P2—C41 | 1.847 (3) | C34—C35 | 1.411 (5) |
P2—C21 | 1.848 (3) | C34—C39 | 1.430 (4) |
O1—C9 | 1.388 (4) | C35—C36 | 1.377 (6) |
O1—C12 | 1.422 (5) | C35—H35A | 0.9500 |
O2—C16 | 1.358 (4) | C36—C37 | 1.400 (4) |
O2—C19 | 1.433 (4) | C36—H36A | 0.9500 |
N1—H1C | 0.88 (4) | C37—C38 | 1.367 (5) |
N1—H1B | 0.96 (5) | C37—H37A | 0.9500 |
N1—C1 | 1.493 (4) | C38—C39 | 1.414 (5) |
N2—H2B | 0.76 (3) | C38—H38A | 0.9500 |
N2—H2A | 0.95 (4) | C41—C46 | 1.384 (5) |
N2—C2 | 1.508 (4) | C41—C42 | 1.414 (5) |
C1—C3 | 1.550 (5) | C42—C43 | 1.387 (5) |
C1—C2 | 1.564 (4) | C42—H42A | 0.9500 |
C1—H1A | 1.0000 | C43—C44 | 1.394 (5) |
C2—C13 | 1.521 (4) | C43—H43A | 0.9500 |
C2—C6 | 1.525 (4) | C44—C45 | 1.374 (6) |
C3—C4 | 1.534 (5) | C44—H44A | 0.9500 |
C3—C5 | 1.548 (5) | C45—C46 | 1.389 (5) |
C3—H3A | 1.0000 | C45—H45A | 0.9500 |
C4—H4A | 0.9800 | C46—H46A | 0.9500 |
C4—H4B | 0.9800 | C51—C52 | 1.387 (5) |
C4—H4C | 0.9800 | C51—C56 | 1.391 (5) |
C5—H5A | 0.9800 | C52—C53 | 1.405 (6) |
C5—H5B | 0.9800 | C52—H52A | 0.9500 |
C5—H5C | 0.9800 | C53—C54 | 1.369 (7) |
C6—C7 | 1.386 (5) | C53—H53A | 0.9500 |
C6—C11 | 1.423 (5) | C54—C55 | 1.380 (7) |
C7—C8 | 1.397 (5) | C54—H54A | 0.9500 |
C7—H7A | 0.9500 | C55—C56 | 1.396 (5) |
C8—C9 | 1.395 (5) | C55—H55A | 0.9500 |
C8—H8A | 0.9500 | C56—H56A | 0.9500 |
C9—C10 | 1.390 (5) | C61—C66 | 1.382 (5) |
C10—C11 | 1.395 (4) | C61—C62 | 1.406 (5) |
C10—H10A | 0.9500 | C62—C63 | 1.390 (5) |
C12—H12A | 0.9800 | C62—H62A | 0.9500 |
C12—H12B | 0.9800 | C63—C64 | 1.378 (6) |
C12—H12C | 0.9800 | C63—H63A | 0.9500 |
C13—C14 | 1.387 (4) | C64—C65 | 1.373 (6) |
C13—C18 | 1.405 (5) | C64—H64A | 0.9500 |
C14—C15 | 1.395 (5) | C65—C66 | 1.388 (6) |
C14—H14A | 0.9500 | C65—H65A | 0.9500 |
C15—C16 | 1.388 (5) | C66—H66A | 0.9500 |
C15—H15A | 0.9500 | C71—C72 | 1.387 (5) |
C16—C17 | 1.399 (5) | C71—C76 | 1.408 (5) |
C17—C18 | 1.379 (5) | C72—C73 | 1.398 (5) |
C17—H17A | 0.9500 | C72—H72A | 0.9500 |
C18—H18A | 0.9500 | C73—C74 | 1.374 (5) |
C19—H19A | 0.9800 | C73—H73A | 0.9500 |
C19—H19B | 0.9800 | C74—C75 | 1.389 (6) |
C19—H19C | 0.9800 | C74—H74A | 0.9500 |
C20—C21 | 1.389 (4) | C75—C76 | 1.390 (5) |
C20—C29 | 1.437 (4) | C75—H75A | 0.9500 |
C20—C30 | 1.500 (4) | C76—H76A | 0.9500 |
C21—C22 | 1.425 (4) | C1S—C2S | 1.3900 |
C22—C23 | 1.363 (4) | C1S—C6S | 1.3900 |
C22—H22A | 0.9500 | C1S—H1SA | 0.9500 |
C23—C24 | 1.407 (5) | C2S—C3S | 1.3900 |
C23—H23A | 0.9500 | C2S—H2SA | 0.9500 |
C24—C25 | 1.424 (5) | C3S—C4S | 1.3900 |
C24—C29 | 1.424 (5) | C3S—H3SA | 0.9500 |
C25—C26 | 1.340 (5) | C4S—C5S | 1.3900 |
C25—H25A | 0.9500 | C4S—H4SA | 0.9500 |
C26—C27 | 1.412 (6) | C5S—C6S | 1.3900 |
C26—H26A | 0.9500 | C5S—H5SA | 0.9500 |
C27—C28 | 1.367 (5) | C6S—H6SA | 0.9500 |
H1RU—Ru1—C11 | 87.1 (12) | C26—C25—H25A | 119.3 |
H1RU—Ru1—N1 | 92.4 (11) | C24—C25—H25A | 119.3 |
C11—Ru1—N1 | 79.53 (12) | C25—C26—C27 | 120.0 (3) |
H1RU—Ru1—N2 | 160.8 (12) | C25—C26—H26A | 120.0 |
C11—Ru1—N2 | 75.93 (12) | C27—C26—H26A | 120.0 |
N1—Ru1—N2 | 75.76 (10) | C28—C27—C26 | 120.5 (3) |
H1RU—Ru1—P1 | 88.4 (11) | C28—C27—H27A | 119.7 |
C11—Ru1—P1 | 92.01 (8) | C26—C27—H27A | 119.7 |
N1—Ru1—P1 | 171.43 (9) | C27—C28—C29 | 121.0 (3) |
N2—Ru1—P1 | 101.01 (8) | C27—C28—H28A | 119.5 |
H1RU—Ru1—P2 | 84.1 (12) | C29—C28—H28A | 119.5 |
C11—Ru1—P2 | 168.64 (8) | C28—C29—C24 | 118.2 (3) |
N1—Ru1—P2 | 93.57 (9) | C28—C29—C20 | 122.4 (3) |
N2—Ru1—P2 | 111.33 (8) | C24—C29—C20 | 119.4 (3) |
P1—Ru1—P2 | 95.00 (3) | C31—C30—C39 | 121.2 (3) |
C61—P1—C71 | 103.52 (15) | C31—C30—C20 | 124.6 (3) |
C61—P1—C31 | 102.32 (16) | C39—C30—C20 | 114.0 (3) |
C71—P1—C31 | 96.82 (14) | C30—C31—C32 | 117.8 (3) |
C61—P1—Ru1 | 108.53 (11) | C30—C31—P1 | 120.4 (2) |
C71—P1—Ru1 | 121.91 (11) | C32—C31—P1 | 121.9 (3) |
C31—P1—Ru1 | 120.94 (10) | C33—C32—C31 | 122.0 (3) |
C51—P2—C41 | 102.20 (14) | C33—C32—H32A | 119.0 |
C51—P2—C21 | 99.88 (15) | C31—C32—H32A | 119.0 |
C41—P2—C21 | 104.05 (14) | C32—C33—C34 | 121.3 (3) |
C51—P2—Ru1 | 126.36 (12) | C32—C33—H33A | 119.4 |
C41—P2—Ru1 | 111.59 (11) | C34—C33—H33A | 119.4 |
C21—P2—Ru1 | 110.25 (10) | C35—C34—C33 | 122.5 (3) |
C9—O1—C12 | 117.3 (3) | C35—C34—C39 | 119.1 (3) |
C16—O2—C19 | 118.0 (3) | C33—C34—C39 | 118.3 (3) |
H1C—N1—H1B | 104 (4) | C36—C35—C34 | 121.3 (3) |
H1C—N1—C1 | 114 (3) | C36—C35—H35A | 119.3 |
H1B—N1—C1 | 110 (3) | C34—C35—H35A | 119.3 |
H1C—N1—Ru1 | 97 (3) | C35—C36—C37 | 119.4 (4) |
H1B—N1—Ru1 | 117 (3) | C35—C36—H36A | 120.3 |
C1—N1—Ru1 | 114.41 (19) | C37—C36—H36A | 120.3 |
H2B—N2—H2A | 102 (3) | C38—C37—C36 | 120.8 (4) |
H2B—N2—C2 | 110 (3) | C38—C37—H37A | 119.6 |
H2A—N2—C2 | 113 (2) | C36—C37—H37A | 119.6 |
H2B—N2—Ru1 | 119 (3) | C37—C38—C39 | 121.5 (3) |
H2A—N2—Ru1 | 109 (2) | C37—C38—H38A | 119.2 |
C2—N2—Ru1 | 103.85 (19) | C39—C38—H38A | 119.2 |
N1—C1—C3 | 113.6 (3) | C38—C39—C34 | 117.8 (3) |
N1—C1—C2 | 107.3 (2) | C38—C39—C30 | 123.1 (3) |
C3—C1—C2 | 115.3 (3) | C34—C39—C30 | 119.1 (3) |
N1—C1—H1A | 106.7 | C46—C41—C42 | 117.8 (3) |
C3—C1—H1A | 106.7 | C46—C41—P2 | 122.8 (2) |
C2—C1—H1A | 106.7 | C42—C41—P2 | 119.0 (2) |
N2—C2—C13 | 109.1 (3) | C43—C42—C41 | 120.9 (3) |
N2—C2—C6 | 104.8 (2) | C43—C42—H42A | 119.6 |
C13—C2—C6 | 114.7 (3) | C41—C42—H42A | 119.6 |
N2—C2—C1 | 104.1 (3) | C42—C43—C44 | 120.0 (3) |
C13—C2—C1 | 113.8 (2) | C42—C43—H43A | 120.0 |
C6—C2—C1 | 109.3 (3) | C44—C43—H43A | 120.0 |
C4—C3—C5 | 109.1 (3) | C45—C44—C43 | 119.2 (3) |
C4—C3—C1 | 109.7 (3) | C45—C44—H44A | 120.4 |
C5—C3—C1 | 114.4 (3) | C43—C44—H44A | 120.4 |
C4—C3—H3A | 107.8 | C44—C45—C46 | 121.1 (4) |
C5—C3—H3A | 107.8 | C44—C45—H45A | 119.5 |
C1—C3—H3A | 107.8 | C46—C45—H45A | 119.5 |
C3—C4—H4A | 109.5 | C41—C46—C45 | 121.0 (3) |
C3—C4—H4B | 109.5 | C41—C46—H46A | 119.5 |
H4A—C4—H4B | 109.5 | C45—C46—H46A | 119.5 |
C3—C4—H4C | 109.5 | C52—C51—C56 | 118.8 (3) |
H4A—C4—H4C | 109.5 | C52—C51—P2 | 118.6 (3) |
H4B—C4—H4C | 109.5 | C56—C51—P2 | 122.2 (3) |
C3—C5—H5A | 109.5 | C51—C52—C53 | 119.9 (4) |
C3—C5—H5B | 109.5 | C51—C52—H52A | 120.1 |
H5A—C5—H5B | 109.5 | C53—C52—H52A | 120.1 |
C3—C5—H5C | 109.5 | C54—C53—C52 | 120.3 (4) |
H5A—C5—H5C | 109.5 | C54—C53—H53A | 119.8 |
H5B—C5—H5C | 109.5 | C52—C53—H53A | 119.8 |
C7—C6—C11 | 121.9 (3) | C53—C54—C55 | 120.7 (4) |
C7—C6—C2 | 122.7 (3) | C53—C54—H54A | 119.7 |
C11—C6—C2 | 115.1 (3) | C55—C54—H54A | 119.7 |
C6—C7—C8 | 121.5 (3) | C54—C55—C56 | 119.1 (4) |
C6—C7—H7A | 119.3 | C54—C55—H55A | 120.4 |
C8—C7—H7A | 119.3 | C56—C55—H55A | 120.4 |
C9—C8—C7 | 117.6 (3) | C51—C56—C55 | 121.2 (4) |
C9—C8—H8A | 121.2 | C51—C56—H56A | 119.4 |
C7—C8—H8A | 121.2 | C55—C56—H56A | 119.4 |
O1—C9—C10 | 116.2 (3) | C66—C61—C62 | 117.4 (3) |
O1—C9—C8 | 123.3 (3) | C66—C61—P1 | 122.8 (3) |
C10—C9—C8 | 120.6 (3) | C62—C61—P1 | 119.1 (3) |
C9—C10—C11 | 123.4 (3) | C63—C62—C61 | 122.0 (4) |
C9—C10—H10A | 118.3 | C63—C62—H62A | 119.0 |
C11—C10—H10A | 118.3 | C61—C62—H62A | 119.0 |
C10—C11—C6 | 115.2 (3) | C64—C63—C62 | 118.7 (4) |
C10—C11—Ru1 | 130.8 (2) | C64—C63—H63A | 120.7 |
C6—C11—Ru1 | 113.7 (2) | C62—C63—H63A | 120.7 |
O1—C12—H12A | 109.5 | C65—C64—C63 | 120.3 (4) |
O1—C12—H12B | 109.5 | C65—C64—H64A | 119.8 |
H12A—C12—H12B | 109.5 | C63—C64—H64A | 119.8 |
O1—C12—H12C | 109.5 | C64—C65—C66 | 120.8 (4) |
H12A—C12—H12C | 109.5 | C64—C65—H65A | 119.6 |
H12B—C12—H12C | 109.5 | C66—C65—H65A | 119.6 |
C14—C13—C18 | 117.3 (3) | C61—C66—C65 | 120.7 (4) |
C14—C13—C2 | 123.5 (3) | C61—C66—H66A | 119.7 |
C18—C13—C2 | 119.0 (3) | C65—C66—H66A | 119.7 |
C13—C14—C15 | 122.2 (3) | C72—C71—C76 | 118.6 (3) |
C13—C14—H14A | 118.9 | C72—C71—P1 | 119.6 (2) |
C15—C14—H14A | 118.9 | C76—C71—P1 | 121.4 (3) |
C16—C15—C14 | 119.3 (3) | C71—C72—C73 | 120.6 (3) |
C16—C15—H15A | 120.3 | C71—C72—H72A | 119.7 |
C14—C15—H15A | 120.3 | C73—C72—H72A | 119.7 |
O2—C16—C15 | 125.0 (3) | C74—C73—C72 | 120.5 (4) |
O2—C16—C17 | 115.6 (3) | C74—C73—H73A | 119.7 |
C15—C16—C17 | 119.4 (3) | C72—C73—H73A | 119.7 |
C18—C17—C16 | 120.3 (3) | C73—C74—C75 | 119.7 (3) |
C18—C17—H17A | 119.9 | C73—C74—H74A | 120.2 |
C16—C17—H17A | 119.9 | C75—C74—H74A | 120.2 |
C17—C18—C13 | 121.3 (3) | C74—C75—C76 | 120.3 (3) |
C17—C18—H18A | 119.3 | C74—C75—H75A | 119.8 |
C13—C18—H18A | 119.3 | C76—C75—H75A | 119.8 |
O2—C19—H19A | 109.5 | C75—C76—C71 | 120.3 (3) |
O2—C19—H19B | 109.5 | C75—C76—H76A | 119.9 |
H19A—C19—H19B | 109.5 | C71—C76—H76A | 119.9 |
O2—C19—H19C | 109.5 | C2S—C1S—C6S | 120.0 |
H19A—C19—H19C | 109.5 | C2S—C1S—H1SA | 120.0 |
H19B—C19—H19C | 109.5 | C6S—C1S—H1SA | 120.0 |
C21—C20—C29 | 120.2 (3) | C1S—C2S—C3S | 120.0 |
C21—C20—C30 | 123.9 (3) | C1S—C2S—H2SA | 120.0 |
C29—C20—C30 | 115.6 (3) | C3S—C2S—H2SA | 120.0 |
C20—C21—C22 | 118.4 (3) | C4S—C3S—C2S | 120.0 |
C20—C21—P2 | 118.6 (2) | C4S—C3S—H3SA | 120.0 |
C22—C21—P2 | 122.5 (2) | C2S—C3S—H3SA | 120.0 |
C23—C22—C21 | 121.8 (3) | C3S—C4S—C5S | 120.0 |
C23—C22—H22A | 119.1 | C3S—C4S—H4SA | 120.0 |
C21—C22—H22A | 119.1 | C5S—C4S—H4SA | 120.0 |
C22—C23—C24 | 121.0 (3) | C6S—C5S—C4S | 120.0 |
C22—C23—H23A | 119.5 | C6S—C5S—H5SA | 120.0 |
C24—C23—H23A | 119.5 | C4S—C5S—H5SA | 120.0 |
C23—C24—C25 | 122.4 (3) | C5S—C6S—C1S | 120.0 |
C23—C24—C29 | 118.8 (3) | C5S—C6S—H6SA | 120.0 |
C25—C24—C29 | 118.8 (3) | C1S—C6S—H6SA | 120.0 |
C26—C25—C24 | 121.5 (3) |
Experimental details
Crystal data | |
Chemical formula | [Ru(C19H25N2O2)H(C44H32P2)]·C6H6 |
Mr | 1116.23 |
Crystal system, space group | Monoclinic, C2 |
Temperature (K) | 150 |
a, b, c (Å) | 38.8848 (8), 13.5741 (3), 10.8871 (2) |
β (°) | 103.967 (1) |
V (Å3) | 5576.6 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.39 |
Crystal size (mm) | 0.35 × 0.32 × 0.25 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.876, 0.909 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 21246, 11534, 10079 |
Rint | 0.051 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.089, 1.04 |
No. of reflections | 11534 |
No. of parameters | 698 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.54, −0.54 |
Absolute structure | Flack (1983), 4924 Friedel pairs |
Absolute structure parameter | −0.045 (19) |
Computer programs: COLLECT (Nonius, 2002), DENZO-SMN (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), SHELXTL (Sheldrick, 2008).
Acknowledgements
The authors wish to acknowledge NSERC Canada and the University of Toronto for funding and donors of the American Chemical Society Petroleum Research Fund for partial support of this research.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Asymmetric hydrogenation of ketones and imines constitute a very valuable technology for the production of chiral alcohols and amines which are useful precursors and end products in the pharmaceutical, agrochemical, fragrance and flavor industries. A variety of useful catalysts have been developed that are broadly applicable, very active and highly selective. These include ruthenium complexes of the type RuCl2(diphosphine)(diamine) originally developed by Noyori and coworkers for ketone hydrogenation processes (Ohkuma et al., 1995; Doucet et al., 1998). Our research (Abdur-Rashid et al., 2000; Abdur-Rashid, Lough et al., 2001) and that of others (Cobley & Henschke, 2003) demonstrated that these catalysts were also capable of reducing imines to amines, including the production of single isomer chiral products. There have been extensive investigations towards isolating and understanding the nature of the active catalytic species generated from RuCl2(diphosphine)(diamine) under the reaction conditions of added base in the presence of hydrogen gas. Our seminal papers (Abdur-Rashid, Faatz et al., 2001; Abdur-Rashid et al., 2002; Abbel et al., 2005) proved that the active catalysts are ruthenium dihydride compounds and demonstrated the role of the bifunctional cis-Ru—H···H—N motif to provide nascent, polarized dihydrogen (Hδ+···Hδ-) for the catalytic ionic hydrogenation of polar C═O and C═N bonds. Our research also resulted in the unprecedented isolation and characterization of stable hydridoamido intermediates and proved that these species are responsible for the rapid heterolytic activation and splitting of hydrogen gas (Abdur-Rashid, Faatz et al., 2001; Abdur-Rashid, et al., 2002). Recently Ohkuma and coworkers reported chlororuthenabicyclic compounds (Matsumura et al., 2011) which are derived from ruthenium complexes containing a chiral diphosphine and the chiral diamine ligand daipen. The work demonstrated that in the presence of base and hydrogen gas these ruthenabicyclic compounds are very useful for the hydrogenation of a wide variety of ketones and are capable of producing chiral alcohols with high enantioselectivities. The authors proposed a mechanism based on a hydridoruthenabicyclic catalytic species. However, their attempts to isolate and characterize this species were not successful. We previously reported the preparation and characterization of the trans-dihydride complex RuH2(R-binap)(R-daipen) (1) (Fig. 1), [R-Binap = (R)-bis(diphenylphosphanyl)-1,1-binaphthyl and R-Daipen = (R)-1,1-bis(4-methoxyphenyl)-3-methylbutane-1,2-diamine] and proved that this compound was an active base-free catalyst for the hydrogenation of ketones in the presence of hydrogen gas (Abdur-Rashid, Faatz et al., 2001).
The title compound (I) was readily obtained from (1) by the loss of hydrogen upon stirring a suspension of (1) in hexanes for 48 h at room temperature under an atmosphere of argon. It was demonstrated that the novel hydridoruthenabicyclic compound (I) is also a very effective base-free catalyst for the hydrogenation of ketones to alcohols. For example, a catalytic amount of (I) resulted in the complete conversion of neat acetophenone (S:C = 2000:1) to (S)-1-phenylethanol (92% e.e.) within 12 h at room temperature in the presence of hydrogen gas (3 atm.).
The molecular structure of complex (I) is shown in Fig. 2. The RuII ion is in a distorted octahedral coordination environment with the hydride H atom (H1RU) trans to the tertiary carbinamine nitrogen atom (N2) giving an H1RU—Ru1—N2 angle of 160.8 (12)°. The equatorial sites are occupied by two phosphorus atoms (P1 and P2), the secondary carbinamine nitrogen atom (N1) and a coordinated carbon atom (C11). The geometric parameters in (I) are comparable to related structures (Guo et al., 2004; Li et al., 2004).