supplementary materials


hp2045 scheme

Acta Cryst. (2012). E68, m1224-m1225    [ doi:10.1107/S1600536812036665 ]

rac-cis-Dicarbonylchlorido{1-[2-(diphenylphosphanyl-[kappa]P)benzyl]-3-(phenyl-[kappa]C1)imidazol-2-ylidene-[kappa]C2}ruthenium(II) dichloromethane monosolvate

G. J. Domski, W. H. Pecak and D. C. Swenson

Abstract top

In the title compound, [Ru(C28H22N2P)Cl(CO)2]·CH2Cl2, the RuII atom exhibits a distorted octahedral coordination geometry. The N-phenyl group of the ligand has undergone orthometalation; as a result, the tridentate phosphane-functionalized N-heterocyclic carbene ligand is coordinating in a meridional fashion. This complex is of interest with respect to transfer hydrogenation catalysis and also provides an example of C-H activation behavior in late transition metal complexes. The dichloromethane solvent molecule is disordered over two sets of sites with an occupancy ratio of 0.873 (14):0.127 (14).

Comment top

Donor-functionalized N-heterocyclic carbenes (NHCs) are employed as ancillary ligands for catalytically active transition metals since they have been shown to prevent common decomposition pathways (e.g. reductive elimination) (Cavell & Normand, 2008). Our research has focused on preparing novel ruthenium(II) complexes supported by donor-functionalized NHCs. In particular we have focused on phosphine-functionalized NHCs since both of these moieties are strong σ-donors and have been shown to effectively stabilize ruthenium(II) at catalytically relevant (i.e. elevated) temperatures. The title compound was exceptionally difficult to characterize via 1H and 13C{1H} NMR spectroscopy due to extensive overlapping of peaks in the aromatic regions. In order to establish the three-dimensional structure of this molecule we grew single crystals of the title complex and collected X-ray diffraction data. Upon solving the structure we were surprised to find that the N-phenyl moiety of the ligand had undergone orthometalation. While C—H activation by ruthenium(II) is not without precedent, we had not expected this to happen; it would have been difficult to elucidate this behavior without the aid of X-ray crystallography.

In the solid state, the geometry about ruthenium was distorted octahedral with a C(3)–Ru–C(11) bond angle of 77.79 (12)°. The Ru-carbonyl distances were inequivalent with the Ru–C(2) distance being 0.072 (0) Å longer than the Ru–C(1) distance; this observation is consistent with the stronger trans-influence of the NHC relative to chloride.

Related literature top

For a review of transition metal catalysts supported by donor-functionalized N-heterocyclic carbenes, see: Cavell & Normand (2008). For the first reported synthesis of the imidazolium chloride pro-ligand, see: Wang et al. (2005). For the structure of a similar molecule bearing an N-mesityl moiety that has not undergone orthometalation, see: Domski et al. (2012).

Experimental top

Single crystals suitable for X-ray diffraction studies were grown by vapor diffusion of diethyl ether onto a saturated dichloromethane solution of the title compound.

Refinement top

The preliminary model of the structure was obtained using XS, a direct methods program. Least-squares refining of the model versus. the data was performed with XL computer program. Illustrations were made with the XP program and tables were made with the XCIF program. All are in the SHELXTL v6.1 package. Thermal ellipsoids shown in the illustrations are at the 50% level unless otherwise noted. All non-hydrogen atoms were refined with anisotropic thermal parameters. A disordered dichloromethane molecule is included in the structure. The relative occupancy refined to 0.873 (14):0.127 (14). The two disorder sites were restrained to have the same conformation, Uaniso(C51)=Uaniso(C51'). The anisotropic displacement parameters were restrained with the rigid body(DELU) restraint and the similarity (SIMU) restraint. All H atoms were included with the riding model using the XL program default values. No further restraints or constraints were imposed on the refinement model.

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title complex with ellipsoids drawn at the 50% probability level. Hydrogen atoms and a dichloromethane molecule of crystallization were omitted for clarity.
rac-cis-Dicarbonylchlorido{1-[2-(diphenylphosphanyl- κP)benzyl]-3-(phenyl-κC1)imidazol-2-ylidene- κC2}ruthenium(II) dichloromethane monosolvate top
Crystal data top
[Ru(C28H22N2P)Cl(CO)2]·CH2Cl2Z = 2
Mr = 694.91F(000) = 700
Triclinic, P1Dx = 1.581 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.1600 (9) ÅCell parameters from 5183 reflections
b = 12.1940 (13) Åθ = 1.0–27.9°
c = 14.9713 (16) ŵ = 0.90 mm1
α = 100.109 (5)°T = 210 K
β = 93.560 (5)°Plate, colorless
γ = 93.469 (5)°0.17 × 0.08 × 0.03 mm
V = 1459.9 (3) Å3
Data collection top
Nonius KappaCCD
diffractometer
5349 independent reflections
Radiation source: fine-focus sealed tube4214 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.038
Detector resolution: 9 pixels mm-1θmax = 25.5°, θmin = 2.8°
phi and ω scansh = 99
Absorption correction: multi-scan
(HKL SCALEPACK; Otwinowski & Minor, 1997)
k = 1414
Tmin = 0.862, Tmax = 0.974l = 1818
20414 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.077H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0237P)2 + 1.1613P]
where P = (Fo2 + 2Fc2)/3
5349 reflections(Δ/σ)max = 0.001
383 parametersΔρmax = 0.60 e Å3
22 restraintsΔρmin = 0.45 e Å3
Crystal data top
[Ru(C28H22N2P)Cl(CO)2]·CH2Cl2γ = 93.469 (5)°
Mr = 694.91V = 1459.9 (3) Å3
Triclinic, P1Z = 2
a = 8.1600 (9) ÅMo Kα radiation
b = 12.1940 (13) ŵ = 0.90 mm1
c = 14.9713 (16) ÅT = 210 K
α = 100.109 (5)°0.17 × 0.08 × 0.03 mm
β = 93.560 (5)°
Data collection top
Nonius KappaCCD
diffractometer
5349 independent reflections
Absorption correction: multi-scan
(HKL SCALEPACK; Otwinowski & Minor, 1997)
4214 reflections with I > 2σ(I)
Tmin = 0.862, Tmax = 0.974Rint = 0.038
20414 measured reflectionsθmax = 25.5°
Refinement top
R[F2 > 2σ(F2)] = 0.036H-atom parameters constrained
wR(F2) = 0.077Δρmax = 0.60 e Å3
S = 1.02Δρmin = 0.45 e Å3
5349 reflectionsAbsolute structure: ?
383 parametersFlack parameter: ?
22 restraintsRogers parameter: ?
Special details top

Experimental. The title compound was prepared by allowing 1-phenyl-3-(2-diphenylphosphinobenzyl)-1H-imidazol-3-ium chloride (0.4997 g) (Wang et al., 2005) to react with Ag2O (0.2502 g) in dry, degassed dichloromethane under a nitrogen atmosphere in the absence of light; 4 Å molecular sieves (approximately 0.5 g) were added to the mixture at the beginning of the reaction. After 24 h, the reaction mixture was filtered through CeliteTM under an atmosphere of nitrogen into a flask containing [Ru(CO)3Cl2]2 (0.1340 g); the reaction mixture was allowed to stir for 24 h in the dark. After stirring overnight, the reaction mixture was filtered through CeliteTM under an atmosphere of dry nitrogen and all volatiles were removed in vacuo. The solid residue was purified via column chromatography (SiO2, 40:1 CH2Cl2/MeOH) to furnish a yellow solid. Single crystals of the title compound were grown by dissolving the crude product in the minimum amount of dichloromethane and allowing diethyl ether to slowly evaporate, condense, and diffuse into the dichloromethane solution.

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.

Several low angle reflections were omitted from the final cycles of refinement due to beam-stop shadowing effects.

A disordered dichloromethane molecule is included in the structure. The relative occupancy refined to 0.873 (14):0.127 (14). The two disorder sites were restrained to have the same conformation, Uaniso(C41)=Uaniso(C41'). The anisotropic displacement parameters were restrained with the rigid body restraint and the simu restraint.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ru10.56260 (3)0.10472 (2)0.259925 (18)0.02297 (9)
Cl10.71756 (10)0.21064 (7)0.39873 (5)0.0297 (2)
C10.4406 (4)0.0144 (3)0.1624 (3)0.0310 (8)
O10.3680 (3)0.0442 (2)0.10503 (18)0.0505 (7)
C20.7517 (4)0.1111 (3)0.1890 (2)0.0300 (8)
O20.8606 (3)0.1083 (2)0.14529 (19)0.0503 (7)
C30.3718 (4)0.0743 (2)0.3387 (2)0.0242 (7)
N40.3856 (3)0.0118 (2)0.38523 (18)0.0255 (6)
C50.2468 (4)0.0284 (3)0.4310 (2)0.0306 (8)
H50.22780.08250.46750.037*
C60.1447 (4)0.0482 (3)0.4128 (2)0.0311 (8)
H60.03990.05820.43440.037*
N70.2224 (3)0.1101 (2)0.35618 (18)0.0247 (6)
C80.1486 (4)0.1970 (3)0.3140 (2)0.0272 (8)
H8A0.03050.19470.32290.033*
H8B0.16110.18110.24840.033*
C110.6328 (4)0.0402 (2)0.3096 (2)0.0229 (7)
C120.7679 (4)0.1015 (3)0.2936 (2)0.0312 (8)
H120.84450.08010.25430.037*
C130.7943 (4)0.1942 (3)0.3337 (2)0.0358 (9)
H130.88710.23460.32070.043*
C140.6857 (4)0.2270 (3)0.3922 (2)0.0361 (9)
H140.70400.29010.41860.043*
C150.5489 (4)0.1671 (3)0.4124 (2)0.0315 (8)
H150.47440.18790.45300.038*
C160.5262 (4)0.0757 (3)0.3706 (2)0.0253 (7)
P10.46973 (10)0.27908 (7)0.22565 (6)0.0231 (2)
C210.3631 (4)0.3606 (2)0.3170 (2)0.0233 (7)
C220.2256 (4)0.3134 (3)0.3529 (2)0.0241 (7)
C230.1539 (4)0.3756 (3)0.4245 (2)0.0314 (8)
H230.06110.34420.44750.038*
C240.2149 (4)0.4827 (3)0.4629 (2)0.0354 (9)
H240.16610.52270.51270.043*
C250.3484 (4)0.5304 (3)0.4277 (2)0.0359 (9)
H250.38940.60390.45240.043*
C260.4217 (4)0.4696 (3)0.3557 (2)0.0308 (8)
H260.51310.50250.33250.037*
C310.3271 (4)0.2636 (3)0.1239 (2)0.0248 (7)
C320.1787 (4)0.3131 (3)0.1231 (2)0.0365 (9)
H320.14910.35890.17610.044*
C330.0732 (4)0.2955 (3)0.0446 (3)0.0438 (10)
H330.02800.32860.04500.053*
C340.1160 (5)0.2301 (3)0.0336 (3)0.0462 (11)
H340.04360.21690.08640.055*
C350.2665 (5)0.1840 (3)0.0341 (3)0.0422 (10)
H350.29820.14130.08800.051*
C360.3710 (4)0.2001 (3)0.0444 (2)0.0338 (8)
H360.47250.16750.04350.041*
C410.6282 (4)0.3817 (2)0.2024 (2)0.0254 (7)
C420.7775 (4)0.4017 (3)0.2551 (2)0.0308 (8)
H420.79950.35890.30030.037*
C430.8933 (4)0.4832 (3)0.2419 (3)0.0349 (9)
H430.99220.49730.27900.042*
C440.8630 (4)0.5444 (3)0.1737 (3)0.0380 (9)
H440.94280.59880.16350.046*
C450.7169 (5)0.5257 (3)0.1210 (3)0.0412 (10)
H450.69690.56790.07510.049*
C460.5985 (4)0.4454 (3)0.1349 (2)0.0341 (9)
H460.49820.43370.09900.041*
C510.3690 (10)0.3020 (15)0.1999 (6)0.0623 (17)0.873 (14)
H51A0.40060.36490.22820.075*0.873 (14)
H51B0.46360.24680.20810.075*0.873 (14)
Cl30.3192 (5)0.3489 (3)0.08393 (18)0.0632 (8)0.873 (14)
Cl40.2056 (3)0.2424 (5)0.2530 (3)0.0888 (15)0.873 (14)
C51'0.367 (7)0.296 (11)0.196 (4)0.0623 (17)0.127 (14)
H51C0.47040.32230.21920.075*0.127 (14)
H51D0.39090.22040.18470.075*0.127 (14)
Cl3'0.294 (4)0.384 (3)0.0949 (13)0.087 (5)0.127 (14)
Cl4'0.226 (3)0.293 (3)0.2777 (13)0.094 (6)0.127 (14)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ru10.02152 (15)0.02327 (15)0.02432 (16)0.00118 (11)0.00288 (11)0.00453 (11)
Cl10.0307 (5)0.0306 (5)0.0274 (5)0.0013 (4)0.0017 (4)0.0054 (4)
C10.0274 (19)0.0269 (19)0.043 (2)0.0078 (16)0.0102 (17)0.0122 (18)
O10.0582 (19)0.0437 (16)0.0441 (17)0.0022 (14)0.0087 (15)0.0008 (14)
C20.030 (2)0.0283 (19)0.030 (2)0.0018 (16)0.0002 (17)0.0030 (16)
O20.0388 (16)0.0631 (19)0.0481 (18)0.0039 (14)0.0217 (14)0.0039 (14)
C30.0273 (18)0.0224 (17)0.0222 (18)0.0027 (14)0.0033 (14)0.0013 (14)
N40.0225 (15)0.0248 (15)0.0292 (16)0.0015 (12)0.0050 (12)0.0041 (12)
C50.032 (2)0.0321 (19)0.028 (2)0.0039 (16)0.0085 (16)0.0078 (16)
C60.0265 (19)0.0314 (19)0.036 (2)0.0021 (16)0.0100 (16)0.0060 (16)
N70.0195 (14)0.0251 (15)0.0294 (16)0.0002 (11)0.0072 (12)0.0037 (12)
C80.0207 (17)0.0324 (19)0.0300 (19)0.0039 (14)0.0024 (15)0.0094 (15)
C110.0239 (17)0.0229 (17)0.0205 (17)0.0043 (14)0.0023 (14)0.0037 (14)
C120.0271 (19)0.033 (2)0.033 (2)0.0019 (15)0.0021 (16)0.0051 (16)
C130.031 (2)0.033 (2)0.044 (2)0.0115 (16)0.0010 (17)0.0047 (17)
C140.043 (2)0.0267 (19)0.039 (2)0.0057 (17)0.0032 (18)0.0087 (17)
C150.033 (2)0.0266 (18)0.035 (2)0.0010 (15)0.0010 (16)0.0059 (16)
C160.0247 (18)0.0212 (17)0.0275 (19)0.0026 (14)0.0018 (15)0.0011 (14)
P10.0227 (4)0.0234 (4)0.0232 (5)0.0011 (4)0.0026 (4)0.0045 (4)
C210.0227 (17)0.0233 (17)0.0241 (18)0.0077 (14)0.0011 (14)0.0038 (14)
C220.0214 (17)0.0244 (17)0.0279 (19)0.0081 (14)0.0006 (14)0.0070 (14)
C230.0246 (18)0.037 (2)0.035 (2)0.0095 (15)0.0053 (16)0.0102 (17)
C240.037 (2)0.037 (2)0.031 (2)0.0128 (17)0.0066 (17)0.0027 (17)
C250.039 (2)0.0268 (19)0.040 (2)0.0050 (16)0.0053 (18)0.0015 (17)
C260.0282 (19)0.0265 (18)0.037 (2)0.0016 (15)0.0020 (16)0.0031 (16)
C310.0258 (18)0.0249 (18)0.0243 (18)0.0014 (14)0.0013 (14)0.0071 (15)
C320.034 (2)0.044 (2)0.034 (2)0.0090 (17)0.0017 (17)0.0109 (17)
C330.030 (2)0.060 (3)0.047 (3)0.0102 (19)0.0033 (19)0.023 (2)
C340.049 (3)0.050 (2)0.039 (2)0.006 (2)0.018 (2)0.015 (2)
C350.060 (3)0.034 (2)0.030 (2)0.0030 (19)0.0057 (19)0.0008 (17)
C360.041 (2)0.0298 (19)0.030 (2)0.0033 (16)0.0035 (17)0.0039 (16)
C410.0269 (18)0.0207 (17)0.0279 (19)0.0032 (14)0.0048 (15)0.0009 (14)
C420.0282 (19)0.0305 (19)0.035 (2)0.0023 (15)0.0011 (16)0.0098 (16)
C430.0258 (19)0.031 (2)0.047 (2)0.0009 (16)0.0001 (17)0.0053 (17)
C440.035 (2)0.030 (2)0.049 (2)0.0072 (16)0.0095 (18)0.0071 (18)
C450.048 (2)0.034 (2)0.043 (2)0.0028 (18)0.0022 (19)0.0145 (18)
C460.035 (2)0.034 (2)0.033 (2)0.0031 (16)0.0018 (17)0.0084 (17)
C510.064 (3)0.064 (3)0.053 (3)0.013 (2)0.004 (2)0.006 (2)
Cl30.0649 (14)0.0762 (16)0.0465 (10)0.0169 (12)0.0063 (8)0.0052 (9)
Cl40.0406 (10)0.120 (3)0.0799 (18)0.0128 (13)0.0074 (11)0.0469 (16)
C51'0.064 (3)0.064 (3)0.053 (3)0.013 (2)0.004 (2)0.006 (2)
Cl3'0.079 (8)0.090 (10)0.083 (7)0.027 (8)0.006 (6)0.009 (7)
Cl4'0.065 (9)0.140 (15)0.083 (8)0.005 (10)0.014 (6)0.038 (11)
Geometric parameters (Å, º) top
Ru1—C11.860 (4)C23—H230.9400
Ru1—C21.932 (4)C24—C251.381 (5)
Ru1—C32.065 (3)C24—H240.9400
Ru1—C112.129 (3)C25—C261.386 (5)
Ru1—P12.4265 (9)C25—H250.9400
Ru1—Cl12.4737 (9)C26—H260.9400
C1—O11.127 (4)C31—C361.381 (5)
C2—O21.135 (4)C31—C321.386 (4)
C3—N71.345 (4)C32—C331.391 (5)
C3—N41.364 (4)C32—H320.9400
N4—C51.382 (4)C33—C341.373 (5)
N4—C161.432 (4)C33—H330.9400
C5—C61.340 (5)C34—C351.382 (5)
C5—H50.9400C34—H340.9400
C6—N71.387 (4)C35—C361.386 (5)
C6—H60.9400C35—H350.9400
N7—C81.465 (4)C36—H360.9400
C8—C221.518 (4)C41—C421.394 (4)
C8—H8A0.9800C41—C461.396 (4)
C8—H8B0.9800C42—C431.378 (4)
C11—C121.379 (4)C42—H420.9400
C11—C161.404 (4)C43—C441.384 (5)
C12—C131.391 (5)C43—H430.9400
C12—H120.9400C44—C451.373 (5)
C13—C141.374 (5)C44—H440.9400
C13—H130.9400C45—C461.385 (5)
C14—C151.391 (5)C45—H450.9400
C14—H140.9400C46—H460.9400
C15—C161.387 (4)C51—Cl41.728 (10)
C15—H150.9400C51—Cl31.744 (7)
P1—C311.834 (3)C51—H51A0.9800
P1—C411.836 (3)C51—H51B0.9800
P1—C211.841 (3)C51'—Cl4'1.727 (11)
C21—C261.396 (4)C51'—Cl3'1.744 (8)
C21—C221.409 (4)C51'—H51C0.9800
C22—C231.383 (4)C51'—H51D0.9800
C23—C241.380 (5)
C1—Ru1—C291.19 (14)C22—C21—P1121.2 (2)
C1—Ru1—C387.39 (13)C23—C22—C21119.4 (3)
C2—Ru1—C3171.22 (13)C23—C22—C8118.1 (3)
C1—Ru1—C1189.85 (13)C21—C22—C8122.5 (3)
C2—Ru1—C1193.55 (13)C24—C23—C22121.8 (3)
C3—Ru1—C1177.79 (12)C24—C23—H23119.1
C1—Ru1—P195.28 (10)C22—C23—H23119.1
C2—Ru1—P193.06 (10)C23—C24—C25119.3 (3)
C3—Ru1—P195.70 (9)C23—C24—H24120.3
C11—Ru1—P1171.55 (9)C25—C24—H24120.3
C1—Ru1—Cl1174.32 (10)C24—C25—C26119.8 (3)
C2—Ru1—Cl192.23 (10)C24—C25—H25120.1
C3—Ru1—Cl188.54 (9)C26—C25—H25120.1
C11—Ru1—Cl185.41 (8)C25—C26—C21121.6 (3)
P1—Ru1—Cl189.07 (3)C25—C26—H26119.2
O1—C1—Ru1177.0 (3)C21—C26—H26119.2
O2—C2—Ru1175.9 (3)C36—C31—C32118.8 (3)
N7—C3—N4104.1 (3)C36—C31—P1118.1 (3)
N7—C3—Ru1139.1 (2)C32—C31—P1123.1 (3)
N4—C3—Ru1116.6 (2)C31—C32—C33120.5 (4)
C3—N4—C5111.4 (3)C31—C32—H32119.8
C3—N4—C16116.8 (3)C33—C32—H32119.8
C5—N4—C16131.4 (3)C34—C33—C32120.3 (4)
C6—C5—N4106.2 (3)C34—C33—H33119.8
C6—C5—H5126.9C32—C33—H33119.8
N4—C5—H5126.9C33—C34—C35119.3 (3)
C5—C6—N7107.3 (3)C33—C34—H34120.3
C5—C6—H6126.4C35—C34—H34120.3
N7—C6—H6126.4C34—C35—C36120.5 (4)
C3—N7—C6111.1 (3)C34—C35—H35119.8
C3—N7—C8123.5 (3)C36—C35—H35119.8
C6—N7—C8125.3 (3)C31—C36—C35120.5 (3)
N7—C8—C22112.9 (2)C31—C36—H36119.7
N7—C8—H8A109.0C35—C36—H36119.7
C22—C8—H8A109.0C42—C41—C46118.6 (3)
N7—C8—H8B109.0C42—C41—P1120.5 (2)
C22—C8—H8B109.0C46—C41—P1120.8 (2)
H8A—C8—H8B107.8C43—C42—C41121.0 (3)
C12—C11—C16115.6 (3)C43—C42—H42119.5
C12—C11—Ru1130.3 (2)C41—C42—H42119.5
C16—C11—Ru1114.0 (2)C42—C43—C44119.6 (3)
C11—C12—C13122.0 (3)C42—C43—H43120.2
C11—C12—H12119.0C44—C43—H43120.2
C13—C12—H12119.0C45—C44—C43120.2 (3)
C14—C13—C12120.4 (3)C45—C44—H44119.9
C14—C13—H13119.8C43—C44—H44119.9
C12—C13—H13119.8C44—C45—C46120.6 (3)
C13—C14—C15120.2 (3)C44—C45—H45119.7
C13—C14—H14119.9C46—C45—H45119.7
C15—C14—H14119.9C45—C46—C41120.0 (3)
C16—C15—C14117.7 (3)C45—C46—H46120.0
C16—C15—H15121.2C41—C46—H46120.0
C14—C15—H15121.2Cl4—C51—Cl3111.5 (8)
C15—C16—C11124.0 (3)Cl4—C51—H51A109.3
C15—C16—N4121.3 (3)Cl3—C51—H51A109.3
C11—C16—N4114.7 (3)Cl4—C51—H51B109.3
C31—P1—C41101.78 (14)Cl3—C51—H51B109.3
C31—P1—C21104.91 (14)H51A—C51—H51B108.0
C41—P1—C21102.61 (14)Cl4'—C51'—Cl3'111.4 (9)
C31—P1—Ru1114.52 (10)Cl4'—C51'—H51C109.4
C41—P1—Ru1116.91 (10)Cl3'—C51'—H51C109.4
C21—P1—Ru1114.40 (10)Cl4'—C51'—H51D109.3
C26—C21—C22118.1 (3)Cl3'—C51'—H51D109.3
C26—C21—P1120.6 (2)H51C—C51'—H51D108.0
C1—Ru1—C3—N780.2 (4)Cl1—Ru1—P1—C4163.93 (12)
C11—Ru1—C3—N7170.6 (4)C1—Ru1—P1—C21120.34 (15)
P1—Ru1—C3—N714.8 (3)C2—Ru1—P1—C21148.19 (14)
Cl1—Ru1—C3—N7103.8 (3)C3—Ru1—P1—C2132.44 (14)
C1—Ru1—C3—N494.1 (2)Cl1—Ru1—P1—C2156.00 (11)
C11—Ru1—C3—N43.7 (2)C31—P1—C21—C26111.9 (3)
P1—Ru1—C3—N4170.9 (2)C41—P1—C21—C265.9 (3)
Cl1—Ru1—C3—N481.9 (2)Ru1—P1—C21—C26121.7 (2)
N7—C3—N4—C50.2 (3)C31—P1—C21—C2271.3 (3)
Ru1—C3—N4—C5176.4 (2)C41—P1—C21—C22177.3 (2)
N7—C3—N4—C16172.8 (2)Ru1—P1—C21—C2255.0 (3)
Ru1—C3—N4—C163.3 (3)C26—C21—C22—C230.0 (4)
C3—N4—C5—C60.1 (4)P1—C21—C22—C23176.8 (2)
C16—N4—C5—C6171.7 (3)C26—C21—C22—C8178.1 (3)
N4—C5—C6—N70.1 (4)P1—C21—C22—C85.1 (4)
N4—C3—N7—C60.3 (3)N7—C8—C22—C2392.6 (3)
Ru1—C3—N7—C6175.1 (3)N7—C8—C22—C2189.3 (4)
N4—C3—N7—C8175.0 (3)C21—C22—C23—C241.0 (5)
Ru1—C3—N7—C80.2 (5)C8—C22—C23—C24179.2 (3)
C5—C6—N7—C30.3 (4)C22—C23—C24—C251.8 (5)
C5—C6—N7—C8174.9 (3)C23—C24—C25—C261.5 (5)
C3—N7—C8—C2274.5 (4)C24—C25—C26—C210.6 (5)
C6—N7—C8—C22110.9 (3)C22—C21—C26—C250.2 (5)
C1—Ru1—C11—C1291.5 (3)P1—C21—C26—C25176.6 (3)
C2—Ru1—C11—C120.3 (3)C41—P1—C31—C3676.7 (3)
C3—Ru1—C11—C12178.9 (3)C21—P1—C31—C36176.7 (2)
Cl1—Ru1—C11—C1291.6 (3)Ru1—P1—C31—C3650.4 (3)
C1—Ru1—C11—C1690.8 (2)C41—P1—C31—C32102.9 (3)
C2—Ru1—C11—C16178.0 (2)C21—P1—C31—C323.8 (3)
C3—Ru1—C11—C163.5 (2)Ru1—P1—C31—C32130.0 (2)
Cl1—Ru1—C11—C1686.0 (2)C36—C31—C32—C332.4 (5)
C16—C11—C12—C131.5 (5)P1—C31—C32—C33178.0 (3)
Ru1—C11—C12—C13179.1 (2)C31—C32—C33—C341.0 (5)
C11—C12—C13—C140.7 (5)C32—C33—C34—C351.4 (6)
C12—C13—C14—C150.5 (5)C33—C34—C35—C362.3 (5)
C13—C14—C15—C160.9 (5)C32—C31—C36—C351.6 (5)
C14—C15—C16—C110.1 (5)P1—C31—C36—C35178.8 (3)
C14—C15—C16—N4177.8 (3)C34—C35—C36—C310.8 (5)
C12—C11—C16—C151.1 (5)C31—P1—C41—C42167.7 (3)
Ru1—C11—C16—C15179.1 (2)C21—P1—C41—C4283.9 (3)
C12—C11—C16—N4179.1 (3)Ru1—P1—C41—C4242.1 (3)
Ru1—C11—C16—N42.9 (3)C31—P1—C41—C4615.8 (3)
C3—N4—C16—C15177.9 (3)C21—P1—C41—C4692.6 (3)
C5—N4—C16—C156.5 (5)Ru1—P1—C41—C46141.4 (2)
C3—N4—C16—C110.2 (4)C46—C41—C42—C430.6 (5)
C5—N4—C16—C11171.6 (3)P1—C41—C42—C43176.0 (3)
C1—Ru1—P1—C310.83 (16)C41—C42—C43—C441.7 (5)
C2—Ru1—P1—C3190.64 (15)C42—C43—C44—C451.6 (6)
C3—Ru1—P1—C3188.73 (14)C43—C44—C45—C460.4 (6)
Cl1—Ru1—P1—C31177.17 (12)C44—C45—C46—C410.7 (6)
C1—Ru1—P1—C41119.73 (16)C42—C41—C46—C450.6 (5)
C2—Ru1—P1—C4128.25 (15)P1—C41—C46—C45177.2 (3)
C3—Ru1—P1—C41152.38 (14)
Selected bond lengths (Å) top
Ru1—C11.860 (4)Ru1—C112.129 (3)
Ru1—C21.932 (4)Ru1—P12.4265 (9)
Ru1—C32.065 (3)Ru1—Cl12.4737 (9)
Acknowledgements top

The authors wish to thank Augustana College for financial support. Additionally, GJD would like to thank Samuel Alvarado for early progress on the synthesis of the imidazolium chloride pro-ligands.

references
References top

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