Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107030466/av3094sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107030466/av3094Isup2.hkl |
CCDC reference: 659120
A Schlenk tube was charged with [RuF2(CO)3]4 (250 mg, 0.280 mmol) and 1,2-bis(diphenylphosphino)ethane (1.114 g, 2.800 mmol). Dichloromethane (40 ml) was transferred onto the solids via a cannular, and the solution was stirred under a partial vacuum for 12 h. All volatiles were removed in vacuo. Recrystallization from a chloroform/DCM/hexane solution afforded (I) as an air- and moisture-sensitive yellow powder in 8% yield. m/z (+ FAB) 897 ([M – 2 F]+, 100%), 499 ([M – 2 F – dppe]+, 46). 1H (CDCl3): δ 7.80–7.20 (m, 40H, Ar—CH), 2.60–1.90 (m, 8H, CH2). 19F{1H} (CDCl3): δ -318.2 (q, 2JPF = 19 Hz, RuF). 31P{1H} (CDCl3): δ 49.8 (br s, RuP). νmax (cm-1, solid)L 2919 (br), 1479 (s), 1435 (s), 1094 (s), 741 (br), 691 (br).
All H atoms were refined using a riding model, using the default SHELXL97 parameters (Sheldrick, 1997) and with isotropic displacement parameters of 1.2 times Uiso of the bonded C atom. The displacement parameters of atoms Ru1 and F1 were restrained using the the SHELXL97 commands DELU 0.005 and SIMU. The largest residual electron density peak in the final Fourier difference map is located 0.35 Å from atom Cl3.
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97, PLATON (Spek, 2003), WinGX (Farrugia, 1999) and enCIFer (Allen et al., 2004).
[RuF2(C26H24P2)2]·2CHCl3 | F(000) = 1196 |
Mr = 1174.59 | Dx = 1.498 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 7764 reflections |
a = 11.3274 (8) Å | θ = 2.3–28.4° |
b = 17.8090 (12) Å | µ = 0.78 mm−1 |
c = 12.9556 (9) Å | T = 150 K |
β = 94.885 (1)° | Block, yellow |
V = 2604.0 (3) Å3 | 0.18 × 0.12 × 0.11 mm |
Z = 2 |
Bruker SMART CCD area-detector diffractometer | 6177 independent reflections |
Radiation source: fine-focus sealed tube | 5249 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ϕ and ω scans | θmax = 28.6°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −15→15 |
Tmin = 0.873, Tmax = 0.918 | k = −23→22 |
22716 measured reflections | l = −17→17 |
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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.145 | Constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0799P)2 + 3.0645P] where P = (Fo2 + 2Fc2)/3 |
6177 reflections | (Δ/σ)max = 0.001 |
329 parameters | Δρmax = 1.86 e Å−3 |
0 restraints | Δρmin = −1.60 e Å−3 |
[RuF2(C26H24P2)2]·2CHCl3 | V = 2604.0 (3) Å3 |
Mr = 1174.59 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.3274 (8) Å | µ = 0.78 mm−1 |
b = 17.8090 (12) Å | T = 150 K |
c = 12.9556 (9) Å | 0.18 × 0.12 × 0.11 mm |
β = 94.885 (1)° |
Bruker SMART CCD area-detector diffractometer | 6177 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 5249 reflections with I > 2σ(I) |
Tmin = 0.873, Tmax = 0.918 | Rint = 0.030 |
22716 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.145 | Constrained |
S = 1.05 | Δρmax = 1.86 e Å−3 |
6177 reflections | Δρmin = −1.60 e Å−3 |
329 parameters |
Experimental. Absorption correction based on 12260 reflections; Rint 0.031 before correction and 0.026 after. |
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 | 0.5000 | 0.0000 | 0.0000 | 0.01770 (12) | |
F1 | 0.62387 (15) | 0.03151 (10) | 0.13009 (13) | 0.0215 (4) | |
P1 | 0.47539 (7) | 0.12127 (4) | −0.06703 (6) | 0.02112 (18) | |
P2 | 0.32541 (7) | 0.03129 (5) | 0.07614 (6) | 0.02225 (18) | |
C1 | 0.3144 (3) | 0.13253 (19) | −0.0916 (3) | 0.0265 (7) | |
H1A | 0.2957 | 0.1852 | −0.1115 | 0.041 (11)* | |
H1B | 0.2847 | 0.0996 | −0.1497 | 0.024 (9)* | |
C2 | 0.2536 (3) | 0.1124 (2) | 0.0047 (3) | 0.0295 (7) | |
H2A | 0.1696 | 0.1000 | −0.0156 | 0.045 (12)* | |
H2B | 0.2552 | 0.1565 | 0.0513 | 0.028 (9)* | |
C3 | 0.5263 (3) | 0.19995 (18) | 0.0152 (2) | 0.0259 (7) | |
C4 | 0.6436 (3) | 0.1996 (2) | 0.0557 (3) | 0.0333 (8) | |
H4 | 0.6930 | 0.1581 | 0.0430 | 0.032 (10)* | |
C5 | 0.6891 (4) | 0.2596 (2) | 0.1147 (3) | 0.0416 (9) | |
H5 | 0.7697 | 0.2589 | 0.1417 | 0.056 (14)* | |
C6 | 0.6198 (5) | 0.3196 (2) | 0.1345 (3) | 0.0519 (11) | |
H6 | 0.6523 | 0.3608 | 0.1738 | 0.062 (11)* | |
C7 | 0.5011 (5) | 0.3200 (2) | 0.0968 (4) | 0.0535 (11) | |
H7 | 0.4516 | 0.3608 | 0.1122 | 0.060 (14)* | |
C8 | 0.4548 (4) | 0.2604 (2) | 0.0362 (3) | 0.0386 (8) | |
H8 | 0.3741 | 0.2611 | 0.0093 | 0.046 (12)* | |
C9 | 0.5251 (3) | 0.14645 (19) | −0.1930 (2) | 0.0258 (6) | |
C10 | 0.5828 (3) | 0.2133 (2) | −0.2114 (3) | 0.0324 (7) | |
H10 | 0.5933 | 0.2500 | −0.1581 | 0.045 (12)* | |
C11 | 0.6251 (4) | 0.2269 (2) | −0.3070 (3) | 0.0424 (9) | |
H11 | 0.6645 | 0.2727 | −0.3190 | 0.062 (15)* | |
C12 | 0.6100 (4) | 0.1739 (3) | −0.3848 (3) | 0.0451 (10) | |
H12 | 0.6413 | 0.1826 | −0.4495 | 0.052 (13)* | |
C13 | 0.5494 (4) | 0.1082 (2) | −0.3687 (3) | 0.0411 (9) | |
H13 | 0.5360 | 0.0727 | −0.4232 | 0.054 (13)* | |
C14 | 0.5082 (3) | 0.0939 (2) | −0.2724 (3) | 0.0317 (7) | |
H14 | 0.4682 | 0.0481 | −0.2609 | 0.024 (9)* | |
C15 | 0.2108 (3) | −0.04088 (19) | 0.0673 (3) | 0.0272 (7) | |
C16 | 0.1417 (3) | −0.0510 (2) | −0.0261 (3) | 0.0334 (8) | |
H16 | 0.1473 | −0.0162 | −0.0809 | 0.047 (13)* | |
C17 | 0.0647 (3) | −0.1117 (2) | −0.0396 (3) | 0.0409 (9) | |
H17 | 0.0185 | −0.1183 | −0.1037 | 0.034 (10)* | |
C18 | 0.0553 (3) | −0.1623 (2) | 0.0400 (4) | 0.0434 (9) | |
H18 | 0.0038 | −0.2042 | 0.0302 | 0.062 (15)* | |
C19 | 0.1206 (3) | −0.1520 (2) | 0.1335 (3) | 0.0391 (9) | |
H19 | 0.1120 | −0.1862 | 0.1887 | 0.045 (12)* | |
C20 | 0.1990 (3) | −0.0920 (2) | 0.1477 (3) | 0.0327 (8) | |
H20 | 0.2446 | −0.0857 | 0.2121 | 0.030 (10)* | |
C21 | 0.3266 (3) | 0.06706 (18) | 0.2083 (2) | 0.0276 (7) | |
C22 | 0.2259 (3) | 0.0681 (2) | 0.2631 (3) | 0.0345 (8) | |
H22 | 0.1549 | 0.0449 | 0.2348 | 0.039 (11)* | |
C23 | 0.2295 (4) | 0.1030 (2) | 0.3590 (3) | 0.0426 (10) | |
H23 | 0.1607 | 0.1035 | 0.3962 | 0.048 (12)* | |
C24 | 0.3308 (4) | 0.1368 (2) | 0.4008 (3) | 0.0471 (10) | |
H24 | 0.3325 | 0.1603 | 0.4667 | 0.058 (14)* | |
C25 | 0.4309 (4) | 0.1368 (2) | 0.3469 (3) | 0.0472 (10) | |
H25 | 0.5011 | 0.1606 | 0.3758 | 0.054 (14)* | |
C26 | 0.4296 (4) | 0.1023 (2) | 0.2507 (3) | 0.0368 (8) | |
H26 | 0.4987 | 0.1026 | 0.2139 | 0.033 (10)* | |
C27 | 0.7811 (5) | 0.0563 (3) | 0.3160 (4) | 0.0564 (12) | |
H27 | 0.7271 | 0.0429 | 0.2537 | 0.10 (2)* | |
Cl1 | 0.72268 (15) | 0.01807 (10) | 0.42480 (12) | 0.0760 (4) | |
Cl2 | 0.92062 (13) | 0.01646 (12) | 0.30151 (14) | 0.0912 (6) | |
Cl3 | 0.7900 (3) | 0.15279 (9) | 0.32307 (15) | 0.1564 (14) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ru1 | 0.01756 (18) | 0.01913 (19) | 0.01672 (18) | 0.00091 (12) | 0.00332 (12) | −0.00011 (12) |
F1 | 0.0220 (9) | 0.0195 (8) | 0.0241 (9) | 0.0027 (7) | 0.0084 (7) | 0.0039 (7) |
P1 | 0.0231 (4) | 0.0208 (4) | 0.0197 (4) | 0.0015 (3) | 0.0035 (3) | 0.0011 (3) |
P2 | 0.0206 (4) | 0.0239 (4) | 0.0230 (4) | 0.0019 (3) | 0.0061 (3) | −0.0007 (3) |
C1 | 0.0264 (16) | 0.0274 (16) | 0.0253 (16) | 0.0045 (13) | 0.0003 (12) | 0.0029 (13) |
C2 | 0.0261 (16) | 0.0305 (17) | 0.0328 (18) | 0.0085 (13) | 0.0076 (13) | 0.0053 (14) |
C3 | 0.0341 (17) | 0.0219 (15) | 0.0221 (15) | −0.0023 (13) | 0.0043 (12) | 0.0009 (12) |
C4 | 0.0361 (19) | 0.0315 (18) | 0.0318 (18) | −0.0020 (15) | −0.0007 (14) | 0.0028 (14) |
C5 | 0.048 (2) | 0.038 (2) | 0.037 (2) | −0.0101 (18) | −0.0051 (17) | 0.0013 (16) |
C6 | 0.080 (3) | 0.036 (2) | 0.039 (2) | −0.010 (2) | −0.007 (2) | −0.0095 (17) |
C7 | 0.073 (3) | 0.033 (2) | 0.054 (3) | 0.006 (2) | 0.002 (2) | −0.0160 (19) |
C8 | 0.044 (2) | 0.0307 (19) | 0.040 (2) | 0.0052 (16) | 0.0006 (17) | −0.0043 (16) |
C9 | 0.0285 (16) | 0.0278 (16) | 0.0215 (15) | 0.0039 (13) | 0.0045 (12) | 0.0052 (12) |
C10 | 0.042 (2) | 0.0273 (17) | 0.0287 (17) | −0.0025 (15) | 0.0067 (14) | 0.0043 (14) |
C11 | 0.054 (2) | 0.039 (2) | 0.036 (2) | −0.0070 (18) | 0.0127 (18) | 0.0118 (16) |
C12 | 0.058 (3) | 0.054 (3) | 0.0252 (18) | −0.003 (2) | 0.0123 (17) | 0.0086 (17) |
C13 | 0.053 (2) | 0.048 (2) | 0.0228 (17) | −0.0008 (19) | 0.0058 (16) | −0.0032 (16) |
C14 | 0.0376 (19) | 0.0320 (18) | 0.0254 (17) | −0.0014 (15) | 0.0016 (14) | 0.0022 (14) |
C15 | 0.0193 (14) | 0.0298 (17) | 0.0335 (17) | 0.0001 (12) | 0.0083 (12) | −0.0018 (13) |
C16 | 0.0251 (16) | 0.0382 (19) | 0.0372 (19) | −0.0008 (14) | 0.0045 (14) | −0.0002 (16) |
C17 | 0.0266 (18) | 0.044 (2) | 0.051 (2) | −0.0026 (16) | −0.0010 (16) | −0.0047 (18) |
C18 | 0.0254 (18) | 0.037 (2) | 0.068 (3) | −0.0048 (16) | 0.0021 (17) | 0.0006 (19) |
C19 | 0.0289 (18) | 0.0332 (19) | 0.056 (2) | −0.0016 (15) | 0.0097 (16) | 0.0106 (18) |
C20 | 0.0268 (17) | 0.0334 (18) | 0.039 (2) | 0.0012 (14) | 0.0077 (14) | 0.0015 (15) |
C21 | 0.0345 (17) | 0.0236 (16) | 0.0257 (16) | 0.0066 (13) | 0.0090 (13) | −0.0004 (12) |
C22 | 0.0359 (19) | 0.0364 (19) | 0.0327 (18) | 0.0088 (15) | 0.0124 (15) | 0.0014 (15) |
C23 | 0.055 (2) | 0.045 (2) | 0.0311 (19) | 0.0150 (19) | 0.0195 (18) | 0.0006 (16) |
C24 | 0.069 (3) | 0.044 (2) | 0.029 (2) | 0.012 (2) | 0.0089 (19) | −0.0099 (17) |
C25 | 0.059 (3) | 0.044 (2) | 0.039 (2) | −0.002 (2) | 0.0037 (19) | −0.0147 (18) |
C26 | 0.043 (2) | 0.037 (2) | 0.0308 (18) | −0.0036 (16) | 0.0094 (15) | −0.0067 (15) |
C27 | 0.072 (3) | 0.039 (2) | 0.056 (3) | −0.009 (2) | −0.005 (2) | 0.004 (2) |
Cl1 | 0.0749 (10) | 0.0972 (11) | 0.0567 (8) | 0.0055 (8) | 0.0115 (7) | 0.0064 (7) |
Cl2 | 0.0459 (7) | 0.1385 (15) | 0.0891 (11) | −0.0006 (8) | 0.0063 (7) | 0.0543 (10) |
Cl3 | 0.340 (4) | 0.0365 (7) | 0.0773 (11) | −0.0278 (13) | −0.0689 (17) | 0.0035 (7) |
Ru1—F1i | 2.1729 (18) | C11—H11 | 0.9500 |
Ru1—F1 | 2.1729 (18) | C12—C13 | 1.381 (6) |
Ru1—P1i | 2.3356 (8) | C12—H12 | 0.9500 |
Ru1—P1 | 2.3356 (8) | C13—C14 | 1.392 (5) |
Ru1—P2i | 2.3510 (8) | C13—H13 | 0.9500 |
Ru1—P2 | 2.3510 (8) | C14—H14 | 0.9500 |
P1—C3 | 1.824 (3) | C15—C16 | 1.395 (5) |
P1—C9 | 1.828 (3) | C15—C20 | 1.399 (5) |
P1—C1 | 1.835 (3) | C16—C17 | 1.389 (5) |
P2—C15 | 1.824 (3) | C16—H16 | 0.9500 |
P2—C21 | 1.826 (3) | C17—C18 | 1.381 (6) |
P2—C2 | 1.865 (3) | C17—H17 | 0.9500 |
C1—C2 | 1.518 (4) | C18—C19 | 1.377 (6) |
C1—H1A | 0.9900 | C18—H18 | 0.9500 |
C1—H1B | 0.9900 | C19—C20 | 1.393 (5) |
C2—H2A | 0.9900 | C19—H19 | 0.9500 |
C2—H2B | 0.9900 | C20—H20 | 0.9500 |
C3—C4 | 1.386 (5) | C21—C22 | 1.394 (5) |
C3—C8 | 1.388 (5) | C21—C26 | 1.397 (5) |
C4—C5 | 1.388 (5) | C22—C23 | 1.388 (5) |
C4—H4 | 0.9500 | C22—H22 | 0.9500 |
C5—C6 | 1.363 (6) | C23—C24 | 1.366 (7) |
C5—H5 | 0.9500 | C23—H23 | 0.9500 |
C6—C7 | 1.391 (7) | C24—C25 | 1.381 (6) |
C6—H6 | 0.9500 | C24—H24 | 0.9500 |
C7—C8 | 1.396 (6) | C25—C26 | 1.389 (5) |
C7—H7 | 0.9500 | C25—H25 | 0.9500 |
C8—H8 | 0.9500 | C26—H26 | 0.9500 |
C9—C10 | 1.388 (5) | C27—Cl3 | 1.723 (5) |
C9—C14 | 1.392 (5) | C27—Cl1 | 1.746 (5) |
C10—C11 | 1.387 (5) | C27—Cl2 | 1.757 (6) |
C10—H10 | 0.9500 | C27—H27 | 1.0000 |
C11—C12 | 1.381 (6) | ||
F1i—Ru1—F1 | 180.00 (14) | C14—C9—P1 | 117.5 (3) |
F1i—Ru1—P1i | 95.64 (5) | C11—C10—C9 | 120.3 (3) |
F1—Ru1—P1i | 84.36 (5) | C11—C10—H10 | 119.8 |
F1i—Ru1—P1 | 84.36 (5) | C9—C10—H10 | 119.8 |
F1—Ru1—P1 | 95.64 (5) | C12—C11—C10 | 120.2 (4) |
P1i—Ru1—P1 | 180.000 (15) | C12—C11—H11 | 119.9 |
F1i—Ru1—P2i | 97.13 (5) | C10—C11—H11 | 119.9 |
F1—Ru1—P2i | 82.87 (5) | C11—C12—C13 | 120.0 (3) |
P1i—Ru1—P2i | 81.88 (3) | C11—C12—H12 | 120.0 |
P1—Ru1—P2i | 98.12 (3) | C13—C12—H12 | 120.0 |
F1i—Ru1—P2 | 82.87 (5) | C12—C13—C14 | 119.9 (4) |
F1—Ru1—P2 | 97.13 (5) | C12—C13—H13 | 120.0 |
P1i—Ru1—P2 | 98.12 (3) | C14—C13—H13 | 120.0 |
P1—Ru1—P2 | 81.88 (3) | C9—C14—C13 | 120.2 (3) |
P2i—Ru1—P2 | 180.00 (5) | C9—C14—H14 | 119.9 |
C3—P1—C9 | 103.10 (15) | C13—C14—H14 | 119.9 |
C3—P1—C1 | 106.12 (16) | C16—C15—C20 | 118.7 (3) |
C9—P1—C1 | 101.29 (15) | C16—C15—P2 | 119.3 (3) |
C3—P1—Ru1 | 118.14 (11) | C20—C15—P2 | 121.6 (3) |
C9—P1—Ru1 | 121.52 (11) | C17—C16—C15 | 120.7 (4) |
C1—P1—Ru1 | 104.53 (11) | C17—C16—H16 | 119.7 |
C15—P2—C21 | 104.66 (16) | C15—C16—H16 | 119.7 |
C15—P2—C2 | 103.67 (16) | C18—C17—C16 | 120.0 (4) |
C21—P2—C2 | 99.40 (15) | C18—C17—H17 | 120.0 |
C15—P2—Ru1 | 115.25 (11) | C16—C17—H17 | 120.0 |
C21—P2—Ru1 | 122.49 (11) | C19—C18—C17 | 120.1 (4) |
C2—P2—Ru1 | 108.80 (11) | C19—C18—H18 | 120.0 |
C2—C1—P1 | 110.2 (2) | C17—C18—H18 | 120.0 |
C2—C1—H1A | 109.6 | C18—C19—C20 | 120.5 (4) |
P1—C1—H1A | 109.6 | C18—C19—H19 | 119.8 |
C2—C1—H1B | 109.6 | C20—C19—H19 | 119.8 |
P1—C1—H1B | 109.6 | C19—C20—C15 | 120.1 (4) |
H1A—C1—H1B | 108.1 | C19—C20—H20 | 120.0 |
C1—C2—P2 | 112.4 (2) | C15—C20—H20 | 120.0 |
C1—C2—H2A | 109.1 | C22—C21—C26 | 119.1 (3) |
P2—C2—H2A | 109.1 | C22—C21—P2 | 122.8 (3) |
C1—C2—H2B | 109.1 | C26—C21—P2 | 117.7 (3) |
P2—C2—H2B | 109.1 | C23—C22—C21 | 120.0 (4) |
H2A—C2—H2B | 107.9 | C23—C22—H22 | 120.0 |
C4—C3—C8 | 119.1 (3) | C21—C22—H22 | 120.0 |
C4—C3—P1 | 117.6 (3) | C24—C23—C22 | 120.8 (4) |
C8—C3—P1 | 123.3 (3) | C24—C23—H23 | 119.6 |
C3—C4—C5 | 120.3 (4) | C22—C23—H23 | 119.6 |
C3—C4—H4 | 119.9 | C23—C24—C25 | 119.9 (4) |
C5—C4—H4 | 119.9 | C23—C24—H24 | 120.1 |
C6—C5—C4 | 121.0 (4) | C25—C24—H24 | 120.1 |
C6—C5—H5 | 119.5 | C24—C25—C26 | 120.5 (4) |
C4—C5—H5 | 119.5 | C24—C25—H25 | 119.7 |
C5—C6—C7 | 119.6 (4) | C26—C25—H25 | 119.7 |
C5—C6—H6 | 120.2 | C25—C26—C21 | 119.8 (4) |
C7—C6—H6 | 120.2 | C25—C26—H26 | 120.1 |
C6—C7—C8 | 119.9 (4) | C21—C26—H26 | 120.1 |
C6—C7—H7 | 120.0 | Cl3—C27—Cl1 | 111.8 (3) |
C8—C7—H7 | 120.0 | Cl3—C27—Cl2 | 111.1 (3) |
C3—C8—C7 | 120.2 (4) | Cl1—C27—Cl2 | 109.6 (3) |
C3—C8—H8 | 119.9 | Cl3—C27—H27 | 108.1 |
C7—C8—H8 | 119.9 | Cl1—C27—H27 | 108.1 |
C10—C9—C14 | 119.2 (3) | Cl2—C27—H27 | 108.1 |
C10—C9—P1 | 123.3 (3) | ||
F1i—Ru1—P1—C3 | 165.36 (13) | C6—C7—C8—C3 | 1.3 (7) |
F1—Ru1—P1—C3 | −14.64 (13) | C3—P1—C9—C10 | −2.4 (3) |
P2i—Ru1—P1—C3 | −98.22 (13) | C1—P1—C9—C10 | 107.3 (3) |
P2—Ru1—P1—C3 | 81.78 (13) | Ru1—P1—C9—C10 | −137.7 (3) |
F1i—Ru1—P1—C9 | −65.62 (14) | C3—P1—C9—C14 | 174.8 (3) |
F1—Ru1—P1—C9 | 114.38 (14) | C1—P1—C9—C14 | −75.5 (3) |
P2i—Ru1—P1—C9 | 30.80 (13) | Ru1—P1—C9—C14 | 39.5 (3) |
P2—Ru1—P1—C9 | −149.20 (13) | C14—C9—C10—C11 | −1.3 (5) |
F1i—Ru1—P1—C1 | 47.72 (12) | P1—C9—C10—C11 | 175.8 (3) |
F1—Ru1—P1—C1 | −132.28 (12) | C9—C10—C11—C12 | 0.1 (6) |
P2i—Ru1—P1—C1 | 144.14 (11) | C10—C11—C12—C13 | 2.0 (7) |
P2—Ru1—P1—C1 | −35.86 (11) | C11—C12—C13—C14 | −2.8 (7) |
F1i—Ru1—P2—C15 | 49.13 (13) | C10—C9—C14—C13 | 0.5 (5) |
F1—Ru1—P2—C15 | −130.87 (13) | P1—C9—C14—C13 | −176.8 (3) |
P1i—Ru1—P2—C15 | −45.59 (13) | C12—C13—C14—C9 | 1.5 (6) |
P1—Ru1—P2—C15 | 134.41 (13) | C21—P2—C15—C16 | 145.2 (3) |
F1i—Ru1—P2—C21 | 178.33 (14) | C2—P2—C15—C16 | 41.5 (3) |
F1—Ru1—P2—C21 | −1.67 (14) | Ru1—P2—C15—C16 | −77.3 (3) |
P1i—Ru1—P2—C21 | 83.61 (13) | C21—P2—C15—C20 | −42.2 (3) |
P1—Ru1—P2—C21 | −96.39 (13) | C2—P2—C15—C20 | −145.9 (3) |
F1i—Ru1—P2—C2 | −66.76 (13) | Ru1—P2—C15—C20 | 95.3 (3) |
F1—Ru1—P2—C2 | 113.24 (13) | C20—C15—C16—C17 | −1.4 (5) |
P1i—Ru1—P2—C2 | −161.48 (13) | P2—C15—C16—C17 | 171.4 (3) |
P1—Ru1—P2—C2 | 18.52 (13) | C15—C16—C17—C18 | 0.5 (6) |
C3—P1—C1—C2 | −73.8 (3) | C16—C17—C18—C19 | 1.2 (6) |
C9—P1—C1—C2 | 178.8 (2) | C17—C18—C19—C20 | −1.9 (6) |
Ru1—P1—C1—C2 | 51.8 (2) | C18—C19—C20—C15 | 1.0 (6) |
P1—C1—C2—P2 | −37.6 (3) | C16—C15—C20—C19 | 0.7 (5) |
C15—P2—C2—C1 | −116.1 (3) | P2—C15—C20—C19 | −172.0 (3) |
C21—P2—C2—C1 | 136.2 (3) | C15—P2—C21—C22 | −29.9 (3) |
Ru1—P2—C2—C1 | 7.0 (3) | C2—P2—C21—C22 | 77.0 (3) |
C9—P1—C3—C4 | −81.7 (3) | Ru1—P2—C21—C22 | −163.5 (2) |
C1—P1—C3—C4 | 172.2 (3) | C15—P2—C21—C26 | 157.4 (3) |
Ru1—P1—C3—C4 | 55.4 (3) | C2—P2—C21—C26 | −95.7 (3) |
C9—P1—C3—C8 | 96.4 (3) | Ru1—P2—C21—C26 | 23.8 (3) |
C1—P1—C3—C8 | −9.7 (3) | C26—C21—C22—C23 | −0.8 (5) |
Ru1—P1—C3—C8 | −126.5 (3) | P2—C21—C22—C23 | −173.3 (3) |
C8—C3—C4—C5 | −1.3 (5) | C21—C22—C23—C24 | 0.2 (6) |
P1—C3—C4—C5 | 176.9 (3) | C22—C23—C24—C25 | 0.4 (6) |
C3—C4—C5—C6 | 0.4 (6) | C23—C24—C25—C26 | −0.4 (7) |
C4—C5—C6—C7 | 1.3 (7) | C24—C25—C26—C21 | −0.2 (6) |
C5—C6—C7—C8 | −2.1 (7) | C22—C21—C26—C25 | 0.8 (6) |
C4—C3—C8—C7 | 0.4 (6) | P2—C21—C26—C25 | 173.7 (3) |
P1—C3—C8—C7 | −177.7 (3) |
Symmetry code: (i) −x+1, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [RuF2(C26H24P2)2]·2CHCl3 |
Mr | 1174.59 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 150 |
a, b, c (Å) | 11.3274 (8), 17.8090 (12), 12.9556 (9) |
β (°) | 94.885 (1) |
V (Å3) | 2604.0 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.78 |
Crystal size (mm) | 0.18 × 0.12 × 0.11 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.873, 0.918 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 22716, 6177, 5249 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.674 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.145, 1.05 |
No. of reflections | 6177 |
No. of parameters | 329 |
H-atom treatment | Constrained |
Δρmax, Δρmin (e Å−3) | 1.86, −1.60 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97, PLATON (Spek, 2003), WinGX (Farrugia, 1999) and enCIFer (Allen et al., 2004).
Ru1—F1i | 2.1729 (18) | P1—C1 | 1.835 (3) |
Ru1—P1 | 2.3356 (8) | P2—C2 | 1.865 (3) |
Ru1—P2 | 2.3510 (8) | C1—C2 | 1.518 (4) |
F1—Ru1—P1 | 95.64 (5) | C1—P1—Ru1 | 104.53 (11) |
P1—Ru1—P2 | 81.88 (3) | C2—P2—Ru1 | 108.80 (11) |
Symmetry code: (i) −x+1, −y, −z. |
Synthetic strategies into ruthenium–fluorido complexes, especially those ligated by bidentate phosphanes, often employ toxic thallium-based metathesis reagents (Barthazy et al., 2000), such that alternative routes into ruthenium–fluorido complexes are, therefore, desirable. Previous work has shown that the fluoride bridges in [RuF2(CO)3]4 are amenable to cleavage by a variety of Lewis bases, affording a facile route into ruthenium–fluorido complexes ligated by monodentate phosphanes (Coleman et al., 1997). However, questions regarding how changes in ligand denticity may influence this reaction protocol remain unanswered.
The reaction between [RuF2(CO)3]4 and bis(diphenylphosphino)ethane (dppe) was facile at room temperature, as evidenced by vigorous evolution of carbon monoxide. Multiple recrystallizations from chloroform/DCM and hexane solutions afforded the product [RuF2(dppe)2]·2CHCl3, (I). The coordination geometry can best be described as octahedral, with the Ru atom on a centre of symmetry and the phenyl rings of the ligand backbone adopting a staggered conformation with respect to each other. Although this could be rationalized on steric grounds, the conformation may also be affected by weak secondary bonding interactions between the metal-bound F atoms and the neighbouring aryl rings. Indeed, the H26···F1 non-bonded contact (2.249 Å) suggests weak intra-molecular hydrogen bonding, as has been previously observed in the related complex [RuF2(dppp)2] [dppp is 1,3-bis(diphenylphosphino)propane; Barthazy et al., 2000]. It is noteworthy that two chloroform molecules cocrystallized within the unit cell, and these engage in hydrogen-bonding interactions with the axial F atomss; the distance from atom C27 to atom F1 [2.905 (5) Å] and the H27···F1 hydrogen-bond length (1.911 Å) suggest a fairly strong interaction.
The Ru—P bond lengths [2.3356 (8) and 2.3510 (8) Å] in (I) are in good agreement with those previously reported for the related complex [RuF2(dppp)2] [2.310 (2) Å]. Intriguingly, the Ru—F bond length in (I) [2.1729 (18) Å] is substantially longer than that observed in [RuF2(dppp)2] [2.065 (3) Å]. The participation of the metal-bound F atoms in hydrogen-bonding interactions with the two chloroform molecules may be responsible for this.
Compound (I) represents a rare example of an octahedral fluorido complex ligated only by phosphorus donors. Furthermore, given the ability of fluorine to act as a strong π donor, the adoption of an F-trans-F (not F-trans-P) configuration in (I) is somewhat surprising, since the π-acceptor capability of alkyl and aryl phosphanes is well established (Orpen & Connelly, 1985, 1990). Indeed, the stereochemistry observed in (I) is in direct contrast to that reported for the related complex [RuF2(dppp)2], which assumes an F-trans-P configuration. It is possible that this is associated with the geometrical restrictions imposed by the chelation constraints of the two-C-atom bridge in dppe [in (I)] when compared with the three-C-atom bridge of dppp {in [RuF2(dppp)2]}. However, this trend is not mirrored in chlorine chemistry; both trans-[RuCl2(dppe)2] (Polam & Porter, 1993) and cis-[RuCl2(depe)2] [depe is 1,2-bis(diethylphosphino)ethane; Winter et al., 2000] employ a phosphane with a two-C-atom bridge. It is noteworthy that the related complex [RuF(FHF)(dmpe)2] [dmpe is 1,2-bis(dimethylphosphino)ethane] also adopts an F-trans-P configuration (Kirkham et al., 2001).