metal-organic compounds
Dichlorido(η6-p-cymene)(ethoxydiphenylphosphane)ruthenium(II)
aDepartment of Chemistry, 1253 University of Oregon, Eugene, Oregon 97403-1253, USA
*Correspondence e-mail: dtyler@uoregon.edu
The title compound, [RuCl2(C10H14)(C14H15OP)], is an RuII complex in which an η6-p-cymene ligand, two chloride anions and the P atom of an ethoxydiphenylphosphane ligand form a piano-stool coordination environment about the central RuII atom.
Related literature
For related structures [Ru(η6-p-cymene)Cl2PPh3] and [Ru(η6-p-cymene)Cl2PPhOEt2], see: Elsegood et al. (2006) and Albertin et al. (2010), respectively. For the application of similar complexes as nitrile hydration catalysts, see: Ahmed et al. (2009); Cavarzan et al. (2010); Cadierno et al. (2008); García-Álvarez et al. (2010, 2011); Knapp et al. (2012).
Experimental
Crystal data
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Data collection: SMART (Bruker, 2000); cell SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536812045461/sj5274sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812045461/sj5274Isup2.hkl
The title compound was prepared following literature procedures (Albertin, et al., 2010). The red solid was dissolved in THF under a nitrogen atmosphere, and single crystals were obtained by slow evaporation of THF.
H atoms were found on the residual density and refined with isotropic thermal parameters.
Data collection: SMART (Bruker, 2000); cell
SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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).Fig. 1. The crystal structure of dichloro(η6-p-cymene)(ethoxydiphenylphosphane)ruthenium(II) with 50% probability displacement ellipsoids and the atom-numbering scheme. H atoms are omitted for clarity. |
[RuCl2(C10H14)(C14H15OP)] | F(000) = 1096 |
Mr = 536.41 | Dx = 1.499 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 4833 reflections |
a = 13.1818 (7) Å | θ = 2.2–28.2° |
b = 10.8481 (6) Å | µ = 0.97 mm−1 |
c = 16.6888 (9) Å | T = 173 K |
β = 95.060 (1)° | Plate, red |
V = 2377.2 (2) Å3 | 0.23 × 0.18 × 0.06 mm |
Z = 4 |
Bruker APEX CCD area-detector diffractometer | 5164 independent reflections |
Radiation source: fine-focus sealed tube | 4294 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
ϕ and ω scans | θmax = 27.0°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1995) | h = −12→16 |
Tmin = 0.809, Tmax = 0.944 | k = −13→12 |
15739 measured reflections | l = −20→21 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.030 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.068 | All H-atom parameters refined |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0316P)2 + 0.5053P] where P = (Fo2 + 2Fc2)/3 |
5164 reflections | (Δ/σ)max = 0.002 |
378 parameters | Δρmax = 0.50 e Å−3 |
0 restraints | Δρmin = −0.47 e Å−3 |
[RuCl2(C10H14)(C14H15OP)] | V = 2377.2 (2) Å3 |
Mr = 536.41 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 13.1818 (7) Å | µ = 0.97 mm−1 |
b = 10.8481 (6) Å | T = 173 K |
c = 16.6888 (9) Å | 0.23 × 0.18 × 0.06 mm |
β = 95.060 (1)° |
Bruker APEX CCD area-detector diffractometer | 5164 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1995) | 4294 reflections with I > 2σ(I) |
Tmin = 0.809, Tmax = 0.944 | Rint = 0.028 |
15739 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.068 | All H-atom parameters refined |
S = 1.05 | Δρmax = 0.50 e Å−3 |
5164 reflections | Δρmin = −0.47 e Å−3 |
378 parameters |
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 | 0.922759 (14) | 0.993847 (17) | 0.179893 (11) | 0.02079 (7) | |
Cl1 | 0.85769 (5) | 1.20143 (6) | 0.16713 (4) | 0.03260 (15) | |
Cl2 | 1.08699 (5) | 1.06510 (6) | 0.14859 (4) | 0.02962 (14) | |
P1 | 0.98348 (5) | 1.03105 (5) | 0.31207 (4) | 0.02006 (13) | |
O1 | 0.90032 (12) | 1.01438 (14) | 0.37705 (10) | 0.0244 (4) | |
C1 | 0.76577 (19) | 0.9210 (2) | 0.15958 (17) | 0.0346 (6) | |
C2 | 0.8041 (2) | 0.9389 (3) | 0.08317 (16) | 0.0347 (6) | |
C3 | 0.8954 (2) | 0.8889 (3) | 0.06431 (16) | 0.0335 (6) | |
C4 | 0.95485 (19) | 0.8142 (2) | 0.12134 (15) | 0.0292 (6) | |
C5 | 0.9169 (2) | 0.7927 (2) | 0.19614 (16) | 0.0287 (6) | |
C6 | 0.8235 (2) | 0.8463 (2) | 0.21485 (16) | 0.0307 (6) | |
C7 | 0.6666 (3) | 0.9770 (4) | 0.1789 (3) | 0.0537 (9) | |
C8 | 1.0545 (2) | 0.7606 (3) | 0.09785 (19) | 0.0407 (7) | |
C9 | 1.0331 (3) | 0.6736 (4) | 0.0262 (3) | 0.0617 (10) | |
C10 | 1.1180 (3) | 0.6994 (4) | 0.1653 (3) | 0.0686 (12) | |
C11 | 1.07110 (18) | 0.9129 (2) | 0.35063 (14) | 0.0245 (5) | |
C12 | 1.0370 (2) | 0.8121 (2) | 0.39239 (15) | 0.0319 (6) | |
C13 | 1.1040 (2) | 0.7190 (3) | 0.41857 (18) | 0.0444 (8) | |
C14 | 1.2050 (2) | 0.7263 (3) | 0.40394 (18) | 0.0446 (8) | |
C15 | 1.2399 (2) | 0.8264 (3) | 0.36299 (17) | 0.0403 (7) | |
C16 | 1.1739 (2) | 0.9189 (3) | 0.33660 (16) | 0.0327 (6) | |
C17 | 1.05088 (17) | 1.1723 (2) | 0.34448 (14) | 0.0238 (5) | |
C18 | 1.0912 (2) | 1.1768 (3) | 0.42473 (16) | 0.0336 (6) | |
C19 | 1.1478 (2) | 1.2776 (3) | 0.45319 (18) | 0.0447 (7) | |
C20 | 1.1628 (2) | 1.3750 (3) | 0.40183 (19) | 0.0448 (8) | |
C21 | 1.1217 (2) | 1.3722 (3) | 0.32335 (18) | 0.0384 (7) | |
C22 | 1.0657 (2) | 1.2705 (2) | 0.29405 (16) | 0.0297 (6) | |
C23 | 0.8140 (2) | 1.0977 (3) | 0.37466 (17) | 0.0317 (6) | |
C24 | 0.7362 (2) | 1.0397 (3) | 0.4228 (2) | 0.0446 (8) | |
H2 | 0.770 (2) | 0.993 (2) | 0.0517 (17) | 0.033 (8)* | |
H3 | 0.9204 (18) | 0.910 (2) | 0.0173 (15) | 0.029 (7)* | |
H5 | 0.956 (2) | 0.751 (3) | 0.2361 (16) | 0.038 (8)* | |
H6 | 0.8040 (18) | 0.836 (2) | 0.2656 (15) | 0.027 (7)* | |
H7A | 0.612 (3) | 0.942 (3) | 0.147 (2) | 0.065 (11)* | |
H7B | 0.649 (3) | 0.982 (3) | 0.234 (3) | 0.093 (15)* | |
H7C | 0.667 (2) | 1.058 (3) | 0.1647 (19) | 0.053 (10)* | |
H8 | 1.092 (2) | 0.827 (3) | 0.0773 (19) | 0.059 (10)* | |
H9A | 0.991 (3) | 0.704 (4) | −0.019 (3) | 0.109 (18)* | |
H9B | 0.997 (3) | 0.593 (4) | 0.046 (2) | 0.091 (13)* | |
H9C | 1.100 (3) | 0.650 (3) | 0.010 (2) | 0.072 (11)* | |
H10A | 1.179 (3) | 0.667 (3) | 0.148 (2) | 0.072 (11)* | |
H10B | 1.129 (3) | 0.747 (4) | 0.213 (3) | 0.100 (15)* | |
H10C | 1.077 (2) | 0.625 (3) | 0.1826 (18) | 0.051 (10)* | |
H12 | 0.964 (2) | 0.806 (2) | 0.4018 (15) | 0.036 (7)* | |
H13 | 1.0801 (19) | 0.650 (2) | 0.4488 (15) | 0.033 (7)* | |
H14 | 1.249 (2) | 0.662 (3) | 0.4195 (17) | 0.047 (8)* | |
H15 | 1.309 (2) | 0.828 (3) | 0.3514 (16) | 0.042 (8)* | |
H16 | 1.192 (2) | 0.985 (2) | 0.3115 (16) | 0.029 (7)* | |
H18 | 1.0840 (19) | 1.115 (3) | 0.4602 (16) | 0.036 (8)* | |
H19 | 1.175 (2) | 1.280 (3) | 0.5067 (18) | 0.052 (9)* | |
H20 | 1.202 (2) | 1.435 (3) | 0.4187 (16) | 0.038 (8)* | |
H21 | 1.133 (2) | 1.438 (3) | 0.2895 (18) | 0.050 (9)* | |
H22 | 1.0405 (18) | 1.269 (2) | 0.2397 (15) | 0.026 (7)* | |
H23A | 0.790 (2) | 1.104 (3) | 0.3202 (18) | 0.051 (9)* | |
H23B | 0.8364 (19) | 1.178 (3) | 0.3987 (15) | 0.034 (7)* | |
H24A | 0.709 (3) | 0.965 (3) | 0.396 (2) | 0.063 (11)* | |
H24B | 0.762 (3) | 1.026 (3) | 0.479 (2) | 0.064 (11)* | |
H24C | 0.681 (3) | 1.094 (3) | 0.4211 (19) | 0.067 (11)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ru1 | 0.02214 (11) | 0.02052 (11) | 0.01992 (10) | −0.00193 (8) | 0.00301 (7) | 0.00024 (7) |
Cl1 | 0.0357 (4) | 0.0261 (3) | 0.0359 (3) | 0.0058 (3) | 0.0025 (3) | 0.0038 (3) |
Cl2 | 0.0299 (3) | 0.0306 (3) | 0.0299 (3) | −0.0086 (3) | 0.0110 (3) | −0.0030 (3) |
P1 | 0.0208 (3) | 0.0191 (3) | 0.0207 (3) | 0.0008 (2) | 0.0042 (2) | 0.0004 (2) |
O1 | 0.0241 (9) | 0.0250 (9) | 0.0251 (9) | 0.0060 (7) | 0.0082 (7) | 0.0024 (7) |
C1 | 0.0259 (14) | 0.0330 (15) | 0.0448 (16) | −0.0073 (11) | 0.0019 (12) | −0.0089 (12) |
C2 | 0.0365 (16) | 0.0329 (15) | 0.0321 (15) | −0.0023 (12) | −0.0104 (12) | −0.0027 (12) |
C3 | 0.0435 (16) | 0.0358 (15) | 0.0214 (13) | −0.0113 (12) | 0.0046 (12) | −0.0073 (11) |
C4 | 0.0293 (14) | 0.0235 (13) | 0.0357 (14) | −0.0078 (10) | 0.0072 (11) | −0.0098 (11) |
C5 | 0.0335 (15) | 0.0207 (13) | 0.0312 (14) | −0.0063 (10) | −0.0008 (12) | −0.0019 (10) |
C6 | 0.0343 (15) | 0.0290 (14) | 0.0302 (14) | −0.0125 (11) | 0.0103 (12) | −0.0018 (11) |
C7 | 0.0286 (17) | 0.055 (2) | 0.078 (3) | −0.0012 (15) | 0.0034 (18) | −0.013 (2) |
C8 | 0.0367 (16) | 0.0306 (15) | 0.0564 (19) | −0.0051 (13) | 0.0132 (14) | −0.0133 (14) |
C9 | 0.060 (2) | 0.067 (3) | 0.062 (2) | 0.002 (2) | 0.025 (2) | −0.030 (2) |
C10 | 0.058 (3) | 0.074 (3) | 0.075 (3) | 0.030 (2) | 0.008 (2) | −0.018 (2) |
C11 | 0.0262 (13) | 0.0260 (13) | 0.0215 (12) | 0.0047 (10) | 0.0043 (10) | −0.0031 (10) |
C12 | 0.0340 (15) | 0.0308 (14) | 0.0319 (14) | 0.0081 (11) | 0.0091 (12) | 0.0053 (11) |
C13 | 0.0538 (19) | 0.0371 (17) | 0.0446 (18) | 0.0145 (14) | 0.0173 (15) | 0.0175 (14) |
C14 | 0.0479 (19) | 0.0487 (19) | 0.0380 (16) | 0.0287 (15) | 0.0087 (14) | 0.0106 (14) |
C15 | 0.0295 (15) | 0.0545 (19) | 0.0377 (16) | 0.0183 (13) | 0.0068 (13) | 0.0021 (14) |
C16 | 0.0306 (15) | 0.0373 (16) | 0.0307 (14) | 0.0054 (12) | 0.0060 (11) | 0.0030 (12) |
C17 | 0.0221 (12) | 0.0241 (12) | 0.0256 (12) | 0.0005 (10) | 0.0047 (10) | −0.0040 (10) |
C18 | 0.0402 (16) | 0.0344 (15) | 0.0263 (13) | −0.0053 (12) | 0.0039 (12) | −0.0008 (12) |
C19 | 0.056 (2) | 0.0455 (18) | 0.0320 (16) | −0.0122 (15) | 0.0005 (14) | −0.0122 (14) |
C20 | 0.0526 (19) | 0.0357 (17) | 0.0466 (18) | −0.0199 (15) | 0.0068 (15) | −0.0145 (14) |
C21 | 0.0488 (18) | 0.0270 (15) | 0.0405 (16) | −0.0090 (13) | 0.0107 (13) | −0.0018 (12) |
C22 | 0.0351 (15) | 0.0269 (14) | 0.0272 (13) | −0.0018 (11) | 0.0025 (11) | −0.0022 (11) |
C23 | 0.0311 (15) | 0.0308 (15) | 0.0346 (15) | 0.0120 (11) | 0.0121 (12) | 0.0054 (12) |
C24 | 0.0333 (17) | 0.059 (2) | 0.0442 (19) | 0.0145 (15) | 0.0171 (14) | 0.0121 (16) |
Ru1—C6 | 2.180 (2) | C9—H9C | 0.98 (4) |
Ru1—C5 | 2.201 (2) | C10—H10A | 0.95 (4) |
Ru1—C1 | 2.213 (2) | C10—H10B | 0.95 (4) |
Ru1—C2 | 2.228 (3) | C10—H10C | 1.03 (3) |
Ru1—C4 | 2.237 (2) | C11—C12 | 1.393 (3) |
Ru1—C3 | 2.242 (2) | C11—C16 | 1.397 (3) |
Ru1—P1 | 2.3147 (6) | C12—C13 | 1.386 (4) |
Ru1—Cl2 | 2.3992 (6) | C12—H12 | 0.98 (3) |
Ru1—Cl1 | 2.4124 (6) | C13—C14 | 1.377 (4) |
P1—O1 | 1.6187 (17) | C13—H13 | 0.97 (3) |
P1—C11 | 1.805 (2) | C14—C15 | 1.383 (4) |
P1—C17 | 1.829 (2) | C14—H14 | 0.92 (3) |
O1—C23 | 1.451 (3) | C15—C16 | 1.375 (4) |
C1—C6 | 1.401 (4) | C15—H15 | 0.95 (3) |
C1—C2 | 1.426 (4) | C16—H16 | 0.87 (3) |
C1—C7 | 1.502 (4) | C17—C22 | 1.382 (3) |
C2—C3 | 1.382 (4) | C17—C18 | 1.398 (3) |
C2—H2 | 0.88 (3) | C18—C19 | 1.383 (4) |
C3—C4 | 1.430 (4) | C18—H18 | 0.91 (3) |
C3—H3 | 0.91 (2) | C19—C20 | 1.386 (4) |
C4—C5 | 1.404 (3) | C19—H19 | 0.93 (3) |
C4—C8 | 1.519 (4) | C20—C21 | 1.373 (4) |
C5—C6 | 1.422 (4) | C20—H20 | 0.86 (3) |
C5—H5 | 0.92 (3) | C21—C22 | 1.391 (4) |
C6—H6 | 0.91 (2) | C21—H21 | 0.93 (3) |
C7—H7A | 0.94 (4) | C22—H22 | 0.94 (2) |
C7—H7B | 0.98 (4) | C23—C24 | 1.497 (4) |
C7—H7C | 0.91 (3) | C23—H23A | 0.94 (3) |
C8—C10 | 1.497 (5) | C23—H23B | 1.00 (3) |
C8—C9 | 1.530 (4) | C24—H24A | 0.98 (3) |
C8—H8 | 0.96 (3) | C24—H24B | 0.98 (4) |
C9—H9A | 0.95 (4) | C24—H24C | 0.94 (3) |
C9—H9B | 1.06 (4) | ||
C6—Ru1—C5 | 37.88 (10) | C1—C6—H6 | 120.1 (16) |
C6—Ru1—C1 | 37.18 (10) | C5—C6—H6 | 118.3 (16) |
C5—Ru1—C1 | 67.83 (10) | Ru1—C6—H6 | 124.3 (16) |
C6—Ru1—C2 | 66.27 (10) | C1—C7—H7A | 110 (2) |
C5—Ru1—C2 | 78.12 (10) | C1—C7—H7B | 121 (3) |
C1—Ru1—C2 | 37.45 (10) | H7A—C7—H7B | 109 (3) |
C6—Ru1—C4 | 67.57 (9) | C1—C7—H7C | 108 (2) |
C5—Ru1—C4 | 36.88 (9) | H7A—C7—H7C | 106 (3) |
C1—Ru1—C4 | 80.35 (9) | H7B—C7—H7C | 102 (3) |
C2—Ru1—C4 | 66.31 (10) | C10—C8—C4 | 114.5 (3) |
C6—Ru1—C3 | 78.61 (10) | C10—C8—C9 | 111.5 (3) |
C5—Ru1—C3 | 66.28 (10) | C4—C8—C9 | 109.5 (3) |
C1—Ru1—C3 | 67.02 (10) | C10—C8—H8 | 109.3 (19) |
C2—Ru1—C3 | 36.02 (10) | C4—C8—H8 | 106.9 (19) |
C4—Ru1—C3 | 37.24 (10) | C9—C8—H8 | 104.6 (19) |
C6—Ru1—P1 | 92.19 (7) | C8—C9—H9A | 117 (3) |
C5—Ru1—P1 | 93.92 (7) | C8—C9—H9B | 109 (2) |
C1—Ru1—P1 | 116.63 (7) | H9A—C9—H9B | 106 (3) |
C2—Ru1—P1 | 154.01 (8) | C8—C9—H9C | 106 (2) |
C4—Ru1—P1 | 120.35 (7) | H9A—C9—H9C | 110 (3) |
C3—Ru1—P1 | 157.59 (8) | H9B—C9—H9C | 108 (3) |
C6—Ru1—Cl2 | 150.41 (8) | C8—C10—H10A | 112 (2) |
C5—Ru1—Cl2 | 112.84 (7) | C8—C10—H10B | 115 (3) |
C1—Ru1—Cl2 | 158.61 (7) | H10A—C10—H10B | 112 (3) |
C2—Ru1—Cl2 | 121.18 (8) | C8—C10—H10C | 106.6 (17) |
C4—Ru1—Cl2 | 88.65 (6) | H10A—C10—H10C | 106 (3) |
C3—Ru1—Cl2 | 93.21 (7) | H10B—C10—H10C | 104 (3) |
P1—Ru1—Cl2 | 84.75 (2) | C12—C11—C16 | 118.7 (2) |
C6—Ru1—Cl1 | 119.46 (7) | C12—C11—P1 | 120.77 (18) |
C5—Ru1—Cl1 | 156.97 (7) | C16—C11—P1 | 120.46 (19) |
C1—Ru1—Cl1 | 89.97 (7) | C13—C12—C11 | 120.4 (3) |
C2—Ru1—Cl1 | 87.95 (8) | C13—C12—H12 | 120.1 (16) |
C4—Ru1—Cl1 | 148.65 (7) | C11—C12—H12 | 119.5 (16) |
C3—Ru1—Cl1 | 111.67 (8) | C14—C13—C12 | 120.0 (3) |
P1—Ru1—Cl1 | 90.67 (2) | C14—C13—H13 | 120.1 (15) |
Cl2—Ru1—Cl1 | 90.04 (2) | C12—C13—H13 | 119.8 (15) |
O1—P1—C11 | 97.57 (10) | C13—C14—C15 | 120.2 (3) |
O1—P1—C17 | 103.62 (10) | C13—C14—H14 | 119.6 (18) |
C11—P1—C17 | 102.15 (11) | C15—C14—H14 | 120.2 (18) |
O1—P1—Ru1 | 114.92 (7) | C16—C15—C14 | 120.1 (3) |
C11—P1—Ru1 | 111.87 (8) | C16—C15—H15 | 121.0 (17) |
C17—P1—Ru1 | 123.10 (8) | C14—C15—H15 | 118.8 (17) |
C23—O1—P1 | 119.18 (15) | C15—C16—C11 | 120.6 (3) |
C6—C1—C2 | 117.0 (2) | C15—C16—H16 | 123.9 (18) |
C6—C1—C7 | 121.6 (3) | C11—C16—H16 | 115.5 (18) |
C2—C1—C7 | 121.4 (3) | C22—C17—C18 | 119.6 (2) |
C6—C1—Ru1 | 70.10 (14) | C22—C17—P1 | 123.84 (18) |
C2—C1—Ru1 | 71.82 (15) | C18—C17—P1 | 116.54 (19) |
C7—C1—Ru1 | 130.0 (2) | C19—C18—C17 | 120.3 (3) |
C3—C2—C1 | 122.3 (3) | C19—C18—H18 | 116.4 (17) |
C3—C2—Ru1 | 72.54 (15) | C17—C18—H18 | 123.2 (17) |
C1—C2—Ru1 | 70.73 (15) | C18—C19—C20 | 119.5 (3) |
C3—C2—H2 | 122.3 (19) | C18—C19—H19 | 119.9 (19) |
C1—C2—H2 | 114.8 (19) | C20—C19—H19 | 120.6 (19) |
Ru1—C2—H2 | 123.0 (17) | C21—C20—C19 | 120.4 (3) |
C2—C3—C4 | 120.5 (2) | C21—C20—H20 | 120.2 (19) |
C2—C3—Ru1 | 71.44 (15) | C19—C20—H20 | 119.2 (19) |
C4—C3—Ru1 | 71.21 (14) | C20—C21—C22 | 120.4 (3) |
C2—C3—H3 | 119.4 (16) | C20—C21—H21 | 119.5 (19) |
C4—C3—H3 | 119.8 (16) | C22—C21—H21 | 120.1 (19) |
Ru1—C3—H3 | 125.2 (16) | C17—C22—C21 | 119.7 (2) |
C5—C4—C3 | 118.0 (2) | C17—C22—H22 | 121.4 (15) |
C5—C4—C8 | 123.3 (3) | C21—C22—H22 | 118.8 (15) |
C3—C4—C8 | 118.7 (2) | O1—C23—C24 | 107.2 (2) |
C5—C4—Ru1 | 70.18 (14) | O1—C23—H23A | 105.7 (18) |
C3—C4—Ru1 | 71.56 (14) | C24—C23—H23A | 111.1 (18) |
C8—C4—Ru1 | 130.35 (17) | O1—C23—H23B | 109.4 (15) |
C4—C5—C6 | 120.7 (2) | C24—C23—H23B | 110.2 (15) |
C4—C5—Ru1 | 72.94 (14) | H23A—C23—H23B | 113 (2) |
C6—C5—Ru1 | 70.22 (14) | C23—C24—H24A | 109.7 (19) |
C4—C5—H5 | 120.3 (16) | C23—C24—H24B | 113 (2) |
C6—C5—H5 | 118.6 (16) | H24A—C24—H24B | 113 (3) |
Ru1—C5—H5 | 123.4 (17) | C23—C24—H24C | 107 (2) |
C1—C6—C5 | 121.5 (2) | H24A—C24—H24C | 105 (3) |
C1—C6—Ru1 | 72.72 (15) | H24B—C24—H24C | 109 (3) |
C5—C6—Ru1 | 71.89 (14) | ||
C6—Ru1—P1—O1 | −35.73 (10) | P1—Ru1—C4—C5 | 49.58 (16) |
C5—Ru1—P1—O1 | −73.63 (9) | Cl2—Ru1—C4—C5 | 132.70 (15) |
C1—Ru1—P1—O1 | −6.51 (10) | Cl1—Ru1—C4—C5 | −139.44 (14) |
C2—Ru1—P1—O1 | −2.91 (19) | C6—Ru1—C4—C3 | 100.96 (17) |
C4—Ru1—P1—O1 | −100.89 (10) | C5—Ru1—C4—C3 | 130.2 (2) |
C3—Ru1—P1—O1 | −100.5 (2) | C1—Ru1—C4—C3 | 64.48 (16) |
Cl2—Ru1—P1—O1 | 173.77 (7) | C2—Ru1—C4—C3 | 28.07 (15) |
Cl1—Ru1—P1—O1 | 83.79 (7) | P1—Ru1—C4—C3 | 179.78 (13) |
C6—Ru1—P1—C11 | 74.33 (11) | Cl2—Ru1—C4—C3 | −97.10 (14) |
C5—Ru1—P1—C11 | 36.43 (11) | Cl1—Ru1—C4—C3 | −9.2 (2) |
C1—Ru1—P1—C11 | 103.55 (12) | C6—Ru1—C4—C8 | −146.6 (3) |
C2—Ru1—P1—C11 | 107.15 (19) | C5—Ru1—C4—C8 | −117.4 (3) |
C4—Ru1—P1—C11 | 9.17 (11) | C1—Ru1—C4—C8 | 176.9 (3) |
C3—Ru1—P1—C11 | 9.5 (2) | C2—Ru1—C4—C8 | 140.5 (3) |
Cl2—Ru1—P1—C11 | −76.17 (9) | C3—Ru1—C4—C8 | 112.4 (3) |
Cl1—Ru1—P1—C11 | −166.15 (9) | P1—Ru1—C4—C8 | −67.8 (3) |
C6—Ru1—P1—C17 | −163.51 (12) | Cl2—Ru1—C4—C8 | 15.3 (2) |
C5—Ru1—P1—C17 | 158.59 (11) | Cl1—Ru1—C4—C8 | 103.2 (3) |
C1—Ru1—P1—C17 | −134.29 (12) | C3—C4—C5—C6 | −1.5 (3) |
C2—Ru1—P1—C17 | −130.70 (19) | C8—C4—C5—C6 | 179.5 (2) |
C4—Ru1—P1—C17 | 131.33 (11) | Ru1—C4—C5—C6 | 53.6 (2) |
C3—Ru1—P1—C17 | 131.7 (2) | C3—C4—C5—Ru1 | −55.1 (2) |
Cl2—Ru1—P1—C17 | 45.98 (9) | C8—C4—C5—Ru1 | 125.9 (2) |
Cl1—Ru1—P1—C17 | −43.99 (9) | C6—Ru1—C5—C4 | 132.7 (2) |
C11—P1—O1—C23 | 176.00 (19) | C1—Ru1—C5—C4 | 103.97 (17) |
C17—P1—O1—C23 | 71.5 (2) | C2—Ru1—C5—C4 | 66.18 (16) |
Ru1—P1—O1—C23 | −65.57 (19) | C3—Ru1—C5—C4 | 30.32 (15) |
C5—Ru1—C1—C6 | 29.19 (15) | P1—Ru1—C5—C4 | −138.82 (14) |
C2—Ru1—C1—C6 | 128.8 (2) | Cl2—Ru1—C5—C4 | −52.87 (16) |
C4—Ru1—C1—C6 | 65.40 (16) | Cl1—Ru1—C5—C4 | 120.15 (18) |
C3—Ru1—C1—C6 | 101.78 (17) | C1—Ru1—C5—C6 | −28.68 (15) |
P1—Ru1—C1—C6 | −53.82 (16) | C2—Ru1—C5—C6 | −66.47 (16) |
Cl2—Ru1—C1—C6 | 125.43 (19) | C4—Ru1—C5—C6 | −132.7 (2) |
Cl1—Ru1—C1—C6 | −144.56 (15) | C3—Ru1—C5—C6 | −102.33 (17) |
C6—Ru1—C1—C2 | −128.8 (2) | P1—Ru1—C5—C6 | 88.53 (14) |
C5—Ru1—C1—C2 | −99.58 (17) | Cl2—Ru1—C5—C6 | 174.48 (13) |
C4—Ru1—C1—C2 | −63.37 (17) | Cl1—Ru1—C5—C6 | −12.5 (3) |
C3—Ru1—C1—C2 | −26.99 (16) | C2—C1—C6—C5 | 1.1 (4) |
P1—Ru1—C1—C2 | 177.41 (14) | C7—C1—C6—C5 | 179.5 (3) |
Cl2—Ru1—C1—C2 | −3.3 (3) | Ru1—C1—C6—C5 | −55.1 (2) |
Cl1—Ru1—C1—C2 | 86.67 (16) | C2—C1—C6—Ru1 | 56.2 (2) |
C6—Ru1—C1—C7 | 115.1 (4) | C7—C1—C6—Ru1 | −125.4 (3) |
C5—Ru1—C1—C7 | 144.3 (3) | C4—C5—C6—C1 | 0.6 (4) |
C2—Ru1—C1—C7 | −116.1 (4) | Ru1—C5—C6—C1 | 55.5 (2) |
C4—Ru1—C1—C7 | −179.5 (3) | C4—C5—C6—Ru1 | −54.8 (2) |
C3—Ru1—C1—C7 | −143.1 (3) | C5—Ru1—C6—C1 | −132.7 (2) |
P1—Ru1—C1—C7 | 61.3 (3) | C2—Ru1—C6—C1 | −31.19 (16) |
Cl2—Ru1—C1—C7 | −119.4 (3) | C4—Ru1—C6—C1 | −104.13 (17) |
Cl1—Ru1—C1—C7 | −29.4 (3) | C3—Ru1—C6—C1 | −66.83 (16) |
C6—C1—C2—C3 | −2.0 (4) | P1—Ru1—C6—C1 | 133.78 (15) |
C7—C1—C2—C3 | 179.6 (3) | Cl2—Ru1—C6—C1 | −143.00 (14) |
Ru1—C1—C2—C3 | 53.3 (2) | Cl1—Ru1—C6—C1 | 41.76 (17) |
C6—C1—C2—Ru1 | −55.3 (2) | C1—Ru1—C6—C5 | 132.7 (2) |
C7—C1—C2—Ru1 | 126.3 (3) | C2—Ru1—C6—C5 | 101.47 (17) |
C6—Ru1—C2—C3 | −103.75 (19) | C4—Ru1—C6—C5 | 28.53 (15) |
C5—Ru1—C2—C3 | −65.80 (17) | C3—Ru1—C6—C5 | 65.83 (16) |
C1—Ru1—C2—C3 | −134.7 (3) | P1—Ru1—C6—C5 | −93.57 (14) |
C4—Ru1—C2—C3 | −28.96 (16) | Cl2—Ru1—C6—C5 | −10.3 (2) |
P1—Ru1—C2—C3 | −140.02 (16) | Cl1—Ru1—C6—C5 | 174.42 (12) |
Cl2—Ru1—C2—C3 | 43.85 (19) | C5—C4—C8—C10 | −9.4 (4) |
Cl1—Ru1—C2—C3 | 132.65 (16) | C3—C4—C8—C10 | 171.6 (3) |
C6—Ru1—C2—C1 | 30.98 (16) | Ru1—C4—C8—C10 | 82.1 (4) |
C5—Ru1—C2—C1 | 68.93 (16) | C5—C4—C8—C9 | 116.6 (3) |
C4—Ru1—C2—C1 | 105.77 (18) | C3—C4—C8—C9 | −62.3 (4) |
C3—Ru1—C2—C1 | 134.7 (3) | Ru1—C4—C8—C9 | −151.9 (3) |
P1—Ru1—C2—C1 | −5.3 (3) | O1—P1—C11—C12 | 27.2 (2) |
Cl2—Ru1—C2—C1 | 178.57 (13) | C17—P1—C11—C12 | 132.9 (2) |
Cl1—Ru1—C2—C1 | −92.62 (15) | Ru1—P1—C11—C12 | −93.6 (2) |
C1—C2—C3—C4 | 1.1 (4) | O1—P1—C11—C16 | −155.1 (2) |
Ru1—C2—C3—C4 | 53.6 (2) | C17—P1—C11—C16 | −49.3 (2) |
C1—C2—C3—Ru1 | −52.5 (2) | Ru1—P1—C11—C16 | 84.2 (2) |
C6—Ru1—C3—C2 | 65.11 (18) | C16—C11—C12—C13 | −0.7 (4) |
C5—Ru1—C3—C2 | 102.84 (18) | P1—C11—C12—C13 | 177.0 (2) |
C1—Ru1—C3—C2 | 27.99 (17) | C11—C12—C13—C14 | 0.6 (4) |
C4—Ru1—C3—C2 | 132.9 (2) | C12—C13—C14—C15 | −0.2 (5) |
P1—Ru1—C3—C2 | 132.40 (19) | C13—C14—C15—C16 | −0.1 (5) |
Cl2—Ru1—C3—C2 | −143.59 (16) | C14—C15—C16—C11 | −0.1 (4) |
Cl1—Ru1—C3—C2 | −52.27 (18) | C12—C11—C16—C15 | 0.5 (4) |
C6—Ru1—C3—C4 | −67.78 (15) | P1—C11—C16—C15 | −177.3 (2) |
C5—Ru1—C3—C4 | −30.05 (14) | O1—P1—C17—C22 | −128.6 (2) |
C1—Ru1—C3—C4 | −104.90 (17) | C11—P1—C17—C22 | 130.4 (2) |
C2—Ru1—C3—C4 | −132.9 (2) | Ru1—P1—C17—C22 | 3.9 (2) |
P1—Ru1—C3—C4 | −0.5 (3) | O1—P1—C17—C18 | 53.3 (2) |
Cl2—Ru1—C3—C4 | 83.53 (14) | C11—P1—C17—C18 | −47.7 (2) |
Cl1—Ru1—C3—C4 | 174.85 (12) | Ru1—P1—C17—C18 | −174.27 (16) |
C2—C3—C4—C5 | 0.7 (4) | C22—C17—C18—C19 | −1.5 (4) |
Ru1—C3—C4—C5 | 54.4 (2) | P1—C17—C18—C19 | 176.7 (2) |
C2—C3—C4—C8 | 179.7 (2) | C17—C18—C19—C20 | 1.0 (5) |
Ru1—C3—C4—C8 | −126.5 (2) | C18—C19—C20—C21 | 0.3 (5) |
C2—C3—C4—Ru1 | −53.8 (2) | C19—C20—C21—C22 | −1.1 (5) |
C6—Ru1—C4—C5 | −29.25 (15) | C18—C17—C22—C21 | 0.8 (4) |
C1—Ru1—C4—C5 | −65.72 (16) | P1—C17—C22—C21 | −177.3 (2) |
C2—Ru1—C4—C5 | −102.14 (17) | C20—C21—C22—C17 | 0.5 (4) |
C3—Ru1—C4—C5 | −130.2 (2) | P1—O1—C23—C24 | 163.4 (2) |
Experimental details
Crystal data | |
Chemical formula | [RuCl2(C10H14)(C14H15OP)] |
Mr | 536.41 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 173 |
a, b, c (Å) | 13.1818 (7), 10.8481 (6), 16.6888 (9) |
β (°) | 95.060 (1) |
V (Å3) | 2377.2 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.97 |
Crystal size (mm) | 0.23 × 0.18 × 0.06 |
Data collection | |
Diffractometer | Bruker APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1995) |
Tmin, Tmax | 0.809, 0.944 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15739, 5164, 4294 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.068, 1.05 |
No. of reflections | 5164 |
No. of parameters | 378 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.50, −0.47 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).
Σ angles = sum of P—Ru—Cl1, P—Ru—Cl2, and Cl1—Ru—Cl2 angles. |
Title compound | [Ru(η6-p-cymene)Cl2PPhOEt2]a | [Ru(η6-p-cymene)Cl2PPh3]b | |
Ru—P | 2.3147 (6) | 2.2807 (7) | 2.3438 (6) |
Ru—Cl1 | 2.4124 (6) | 2.4171 (7) | 2.4154 (6) |
Ru—Cl2 | 2.3992 (6) | 2.4038 (7) | 2.4151 (6) |
Ru—C(av) | 2.217 (1) | 2.218 (4) | 2.218 (2) |
P—Ru – Cl1 | 90.67 (2) | 87.59 (2) | 87.094 (19) |
P—Ru – Cl2 | 84.75 (2) | 87.89 (2) | 90.27 (2) |
Cl1—Ru – Cl2 | 90.04 (2) | 88.81 (2) | 88.41 (2) |
Σ angles | 265.46 | 264.29 | 265.77 |
Notes: (a) Albertin et al. (2010); (b) Elsegood et al. (2006). |
Acknowledgements
Acknowledgement is made to the NSF (CHE-0719171) for the support of research carried out in the authors' laboratory. SMMK also wishes to acknowledge the US Department of Education (P200A070436) and the NSF Graduate STEM Fellows in K-12 Education (GK-12) program (DGE-0742540) for additional support.
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.
Investigations in our laboratory have focused on the synthesis and study of nitrile hydration catalysts for the hydration of cyanohydrins (Ahmed et al., 2009). Application of other similar complexes as nitrile hydration catalysts have also been reported (Cavarzan, et al., 2010; Cadierno, et al., 2008; García-Álvarez, et al., 2010, 2011; Knapp, et al., 2012). These catalysts have been found to be susceptible to poisoning by cyanide, which forms when cyanohydrins decompose in aqueous solutions. The title compound [Ru(η6-p-cymene)Cl2PPh2OEt] (1), as well as the similar compounds [Ru(η6-p-cymene)Cl2PPhOEt2], (Albertin, et al., 2010), (2), and [Ru(η6-p- cymene)Cl2PPh3] (3), (Elsegood, et al., 2006), have been used previously to hydrate nitriles in aqueous solutions, where addition of surfactant was used to increase the solubility of the catalyst by promoting the formation of micelles (Cavarzan, et al., 2010). It was hypothesized that a hydrophobic catalyst would be resistant to cyanide poisoning under biphasic conditions, because the cyanide would be in the aqueous phase and the catalyst in the organic phase. Therefore, 1 was synthesized and used as a nitrile hydration catalyst under biphasic conditions using 1,1,2,2-tetrachloroethane at 100 °C. Hydration of the model nitriles acetonitrile and 3-hydroxypropionitrile went to completion within 48 h under these conditions. Unfortunately, no hydration of the cyanohydrins glycolonitrile, lactonitrile, or acetone cyanohydrin was observed.
The structure of complex 1 reported here adopts the classic piano stool structure with a pseudo-tetrahedral arrangement of the p-cymene, chloride anions and the phosphane about the ruthenium metal center. The bond lengths and angles about the Ru core compare well with 2 (Albertin, et al., 2010) and 3 (Elsegood, et al., 2006), which have been investigated previously (Table 1). The average Ru – C distance is 2.217 (3) Å, which is very similar to the previously reported Ru – C distances of 2.218 (4) Å and 2.218 (2) Å for 2 and 3, respectively. The Ru – C bonds trans to the phosphane are lengthened, as has been observed previously (Elsegood, et al., 2006), where Ru – C2 (2.228 (3) Å) and Ru – C3 (2.242 (2) Å) are longer than the other Ru – C bonds (average length 2.208 (3) Å). A comparison of the sum of the P – Ru – Cl1, P – Ru – Cl2, and Cl1 – Ru – Cl2 angles between 1 – 3 indicates that, as expected, 1 is more sterically hindered than 2 and less hindered than 3 (Table 1).