Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107025358/gd3114sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107025358/gd3114Isup2.hkl |
CCDC reference: 619515
[Ir(COD)(PPh3)2]+[BF4]- (100 mg, 0.110 mmol) dissolved in dichloromethane (4 cm3) was cooled to 195 K, and placed under 1100 Torr (1 Torr = 133.322 Pa) of COF2. The solution was warmed to room temperature, and stirred for 3 d whilst the uptake of COF2 was measured tensimetrically. After removal of volatiles in vacuo, the resulting dark solid was washed twice with cold THF (0.5 cm3, 258 K), and the dark solution carefully decanted at 258 K, to afford the product [IrCl2(CO)2(PPh3)2]+[BF4]- (I) as an air-sensitive white solid in 32% yield. m/z (+ FAB) 815 ([M –BF4 –CO]+), 787 ([M –BF4 -2CO]+), 751 ([M –BF4 -2CO –Cl]+), 715 ([M –BF4 -2CO -2 C l]+). 1H (CD2Cl2): δ 7.91–7.40 (m, 30H, ArH); 19F{1H} NMR (CD2Cl2): δ -149.7 (s); 31P{1H} (CD2Cl2): δ -16.2 (s). νmax/cm–1 (solid) 2016 s (CO), 1483 s, 1432 s, 1070 s ([BF4]-), 683 s. Single crystals of (I) suitable for X-ray diffraction were grown by slow vapour diffusion of hexane into a saturated dichloromethane solution of (I).
All H atoms were treated as riding atoms in geometrically idealized positions with C—H distances of 0.95 Å and Uiso(H) = 1.2Ueq(C). The F atoms of the BF4- ion, which lies across a twofold rotation axis, were found to be disordered over two sets of sites. Free refinement of the two possible positions for F1 and F2 gave final occupancies of 0.50 (3) for each, in the positions shown in Fig. 1. A t the end of the refinement, the largest residual electron density peak in the Fourier difference map (1.73 e Å-3) is located 0.97 Å from Ir1.
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); 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).
Fig. 1. ORTEP representation of (I) showing 50% probability ellipsoids. H atoms have been omitted for clarity. [Symmetry code: (i) 1 - x, 1 - y, z]. |
[IrCl2(C18H15P)2(CO)2]BF4 | F(000) = 912 |
Mr = 930.47 | Dx = 1.762 Mg m−3 |
Orthorhombic, P21212 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2 2ab | Cell parameters from 8607 reflections |
a = 11.2488 (5) Å | θ = 2.3–28.0° |
b = 14.6091 (7) Å | µ = 4.11 mm−1 |
c = 10.6711 (5) Å | T = 150 K |
V = 1753.63 (14) Å3 | Block, colourless |
Z = 2 | 0.20 × 0.16 × 0.11 mm |
CCD area-detector diffractometer | 4021 independent reflections |
Radiation source: fine-focus sealed tube | 3873 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.044 |
ϕ and ω scans | θmax = 27.5°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −14→14 |
Tmin = 0.504, Tmax = 0.637 | k = −18→18 |
15288 measured reflections | l = −13→13 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.022 | H-atom parameters constrained |
wR(F2) = 0.046 | w = 1/[σ2(Fo2) + (0.0205P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.99 | (Δ/σ)max = 0.002 |
4021 reflections | Δρmax = 1.47 e Å−3 |
246 parameters | Δρmin = −0.50 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 1721 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.015 (5) |
[IrCl2(C18H15P)2(CO)2]BF4 | V = 1753.63 (14) Å3 |
Mr = 930.47 | Z = 2 |
Orthorhombic, P21212 | Mo Kα radiation |
a = 11.2488 (5) Å | µ = 4.11 mm−1 |
b = 14.6091 (7) Å | T = 150 K |
c = 10.6711 (5) Å | 0.20 × 0.16 × 0.11 mm |
CCD area-detector diffractometer | 4021 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 3873 reflections with I > 2σ(I) |
Tmin = 0.504, Tmax = 0.637 | Rint = 0.044 |
15288 measured reflections |
R[F2 > 2σ(F2)] = 0.022 | H-atom parameters constrained |
wR(F2) = 0.046 | Δρmax = 1.47 e Å−3 |
S = 0.99 | Δρmin = −0.50 e Å−3 |
4021 reflections | Absolute structure: Flack (1983), 1721 Friedel pairs |
246 parameters | Absolute structure parameter: −0.015 (5) |
0 restraints |
Experimental. Absorption correction based on 12102 reflections (SADABS); Rint 0.055 before correction and 0.028 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 > 2σ(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 | Occ. (<1) | |
Ir1 | 0.5000 | 0.5000 | 0.649223 (14) | 0.01932 (5) | |
Cl1 | 0.53239 (7) | 0.38361 (6) | 0.49930 (9) | 0.0295 (2) | |
C1 | 0.4663 (3) | 0.5952 (3) | 0.7668 (3) | 0.0295 (9) | |
O1 | 0.4416 (2) | 0.6546 (2) | 0.8270 (3) | 0.0473 (8) | |
P1 | 0.29079 (7) | 0.46002 (6) | 0.64265 (8) | 0.02045 (17) | |
C2 | 0.2661 (3) | 0.3569 (2) | 0.7344 (3) | 0.0219 (7) | |
C3 | 0.2826 (3) | 0.3597 (2) | 0.8633 (3) | 0.0296 (8) | |
H3 | 0.3044 | 0.4155 | 0.9030 | 0.035* | |
C4 | 0.2673 (3) | 0.2815 (3) | 0.9333 (3) | 0.0373 (9) | |
H4 | 0.2768 | 0.2838 | 1.0217 | 0.045* | |
C5 | 0.2384 (3) | 0.2001 (3) | 0.8767 (4) | 0.0377 (9) | |
H5 | 0.2264 | 0.1466 | 0.9258 | 0.045* | |
C6 | 0.2269 (3) | 0.1963 (2) | 0.7490 (4) | 0.0352 (9) | |
H6 | 0.2094 | 0.1395 | 0.7098 | 0.042* | |
C7 | 0.2403 (3) | 0.2737 (2) | 0.6766 (3) | 0.0278 (8) | |
H7 | 0.2321 | 0.2704 | 0.5881 | 0.033* | |
C8 | 0.2220 (3) | 0.4378 (2) | 0.4911 (3) | 0.0241 (7) | |
C9 | 0.1033 (3) | 0.4078 (3) | 0.4958 (4) | 0.0322 (8) | |
H9 | 0.0639 | 0.4021 | 0.5742 | 0.039* | |
C10 | 0.0446 (3) | 0.3867 (3) | 0.3866 (4) | 0.0405 (10) | |
H10 | −0.0348 | 0.3646 | 0.3901 | 0.049* | |
C11 | 0.0996 (3) | 0.3972 (3) | 0.2725 (4) | 0.0389 (10) | |
H11 | 0.0584 | 0.3826 | 0.1974 | 0.047* | |
C12 | 0.2153 (3) | 0.4292 (3) | 0.2675 (4) | 0.0356 (9) | |
H12 | 0.2527 | 0.4377 | 0.1885 | 0.043* | |
C13 | 0.2768 (3) | 0.4491 (2) | 0.3762 (3) | 0.0278 (8) | |
H13 | 0.3564 | 0.4705 | 0.3720 | 0.033* | |
C14 | 0.1993 (3) | 0.5525 (2) | 0.7067 (3) | 0.0241 (7) | |
C15 | 0.1407 (4) | 0.5492 (3) | 0.8193 (4) | 0.0396 (10) | |
H15 | 0.1441 | 0.4953 | 0.8690 | 0.048* | |
C16 | 0.0767 (4) | 0.6243 (3) | 0.8607 (4) | 0.0491 (11) | |
H16 | 0.0365 | 0.6215 | 0.9389 | 0.059* | |
C17 | 0.0708 (3) | 0.7025 (3) | 0.7902 (4) | 0.0418 (10) | |
H17 | 0.0270 | 0.7538 | 0.8194 | 0.050* | |
C18 | 0.1281 (3) | 0.7061 (3) | 0.6780 (4) | 0.0407 (10) | |
H18 | 0.1246 | 0.7602 | 0.6288 | 0.049* | |
C19 | 0.1914 (3) | 0.6312 (2) | 0.6356 (4) | 0.0342 (9) | |
H19 | 0.2299 | 0.6339 | 0.5565 | 0.041* | |
B1 | 0.5000 | 0.5000 | 0.0845 (4) | 0.0310 (11) | |
F1 | 0.4267 (16) | 0.5216 (7) | −0.0072 (12) | 0.051 (3) | 0.50 (3) |
F2 | 0.5001 (13) | 0.4406 (11) | 0.1829 (11) | 0.049 (3) | 0.50 (3) |
F1' | 0.3790 (12) | 0.5098 (7) | 0.0372 (14) | 0.047 (3) | 0.50 (3) |
F2' | 0.4698 (9) | 0.4108 (7) | 0.127 (2) | 0.054 (4) | 0.50 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ir1 | 0.01548 (7) | 0.01807 (8) | 0.02440 (8) | −0.00194 (12) | 0.000 | 0.000 |
Cl1 | 0.0256 (5) | 0.0245 (4) | 0.0383 (5) | −0.0002 (3) | 0.0004 (3) | −0.0078 (4) |
C1 | 0.0169 (19) | 0.040 (2) | 0.032 (2) | −0.0014 (14) | 0.0005 (13) | −0.0034 (17) |
O1 | 0.0323 (15) | 0.0576 (19) | 0.052 (2) | 0.0042 (13) | −0.0020 (13) | −0.0249 (16) |
P1 | 0.0166 (4) | 0.0189 (4) | 0.0258 (4) | −0.0025 (3) | −0.0002 (4) | 0.0014 (4) |
C2 | 0.0156 (15) | 0.0227 (17) | 0.0273 (18) | −0.0032 (13) | 0.0018 (13) | 0.0038 (14) |
C3 | 0.0279 (18) | 0.0281 (18) | 0.033 (2) | −0.0063 (15) | −0.0059 (16) | 0.0017 (16) |
C4 | 0.044 (2) | 0.042 (2) | 0.025 (2) | −0.0041 (18) | −0.0056 (17) | 0.0095 (17) |
C5 | 0.036 (2) | 0.031 (2) | 0.046 (3) | −0.0058 (16) | −0.0012 (18) | 0.0156 (18) |
C6 | 0.036 (2) | 0.0223 (19) | 0.047 (2) | −0.0060 (16) | −0.0028 (19) | 0.0018 (17) |
C7 | 0.0242 (18) | 0.0268 (18) | 0.032 (2) | 0.0012 (14) | −0.0008 (15) | 0.0021 (15) |
C8 | 0.0223 (16) | 0.0207 (17) | 0.0292 (18) | −0.0010 (13) | −0.0065 (15) | 0.0009 (14) |
C9 | 0.0228 (18) | 0.037 (2) | 0.037 (2) | −0.0051 (15) | −0.0024 (16) | 0.0033 (17) |
C10 | 0.0289 (19) | 0.045 (2) | 0.048 (3) | −0.0080 (17) | −0.0128 (17) | 0.000 (2) |
C11 | 0.039 (2) | 0.040 (2) | 0.037 (2) | −0.0007 (19) | −0.0166 (18) | −0.0055 (19) |
C12 | 0.038 (2) | 0.038 (2) | 0.030 (2) | 0.0003 (18) | −0.0005 (17) | −0.0010 (17) |
C13 | 0.0274 (18) | 0.0226 (18) | 0.033 (2) | −0.0025 (14) | 0.0006 (15) | 0.0028 (15) |
C14 | 0.0187 (16) | 0.0236 (18) | 0.0300 (18) | −0.0005 (13) | −0.0024 (14) | −0.0058 (15) |
C15 | 0.039 (2) | 0.036 (2) | 0.044 (3) | 0.0044 (18) | 0.0074 (18) | 0.0022 (18) |
C16 | 0.043 (2) | 0.054 (3) | 0.050 (3) | 0.010 (2) | 0.012 (2) | −0.014 (2) |
C17 | 0.026 (2) | 0.037 (2) | 0.062 (3) | 0.0092 (17) | −0.0102 (19) | −0.019 (2) |
C18 | 0.031 (2) | 0.026 (2) | 0.065 (3) | 0.0056 (16) | −0.011 (2) | −0.0008 (19) |
C19 | 0.0255 (18) | 0.034 (2) | 0.043 (2) | 0.0056 (15) | 0.0021 (17) | 0.0032 (18) |
B1 | 0.037 (3) | 0.031 (3) | 0.024 (3) | −0.004 (6) | 0.000 | 0.000 |
F1 | 0.057 (6) | 0.049 (5) | 0.046 (5) | 0.010 (4) | −0.017 (4) | −0.012 (3) |
F2 | 0.048 (4) | 0.067 (5) | 0.032 (4) | 0.012 (6) | 0.005 (4) | 0.020 (4) |
F1' | 0.038 (4) | 0.047 (3) | 0.056 (5) | −0.005 (4) | −0.015 (4) | −0.009 (4) |
F2' | 0.045 (4) | 0.042 (4) | 0.073 (9) | 0.000 (3) | 0.011 (4) | 0.027 (5) |
Ir1—C1 | 1.911 (4) | C10—C11 | 1.375 (5) |
Ir1—Cl1 | 2.3629 (8) | C10—H10 | 0.9500 |
Ir1—P1 | 2.4258 (8) | C11—C12 | 1.383 (5) |
C1—O1 | 1.116 (4) | C11—H11 | 0.9500 |
P1—C2 | 1.818 (3) | C12—C13 | 1.382 (5) |
P1—C8 | 1.822 (3) | C12—H12 | 0.9500 |
P1—C14 | 1.831 (3) | C13—H13 | 0.9500 |
C2—C3 | 1.388 (5) | C14—C15 | 1.371 (5) |
C2—C7 | 1.394 (5) | C14—C19 | 1.381 (5) |
C3—C4 | 1.377 (5) | C15—C16 | 1.384 (5) |
C3—H3 | 0.9500 | C15—H15 | 0.9500 |
C4—C5 | 1.373 (5) | C16—C17 | 1.370 (6) |
C4—H4 | 0.9500 | C16—H16 | 0.9500 |
C5—C6 | 1.370 (5) | C17—C18 | 1.360 (6) |
C5—H5 | 0.9500 | C17—H17 | 0.9500 |
C6—C7 | 1.378 (5) | C18—C19 | 1.382 (5) |
C6—H6 | 0.9500 | C18—H18 | 0.9500 |
C7—H7 | 0.9500 | C19—H19 | 0.9500 |
C8—C13 | 1.382 (5) | B1—F1 | 1.318 (8) |
C8—C9 | 1.406 (5) | B1—F2 | 1.361 (7) |
C9—C10 | 1.375 (5) | B1—F2' | 1.421 (7) |
C9—H9 | 0.9500 | B1—F1' | 1.458 (9) |
C1—Ir1—C1i | 97.9 (2) | C8—C9—H9 | 120.1 |
C1—Ir1—Cl1 | 177.16 (10) | C9—C10—C11 | 120.6 (3) |
C1i—Ir1—Cl1 | 83.70 (11) | C9—C10—H10 | 119.7 |
Cl1—Ir1—Cl1i | 94.77 (5) | C11—C10—H10 | 119.7 |
C1—Ir1—P1 | 90.08 (9) | C10—C11—C12 | 119.7 (4) |
C1i—Ir1—P1 | 92.09 (9) | C10—C11—H11 | 120.1 |
Cl1—Ir1—P1 | 87.52 (3) | C12—C11—H11 | 120.1 |
Cl1i—Ir1—P1 | 90.23 (3) | C13—C12—C11 | 120.6 (4) |
P1—Ir1—P1i | 176.68 (4) | C13—C12—H12 | 119.7 |
O1—C1—Ir1 | 173.8 (3) | C11—C12—H12 | 119.7 |
C2—P1—C8 | 105.43 (15) | C8—C13—C12 | 119.8 (3) |
C2—P1—C14 | 108.93 (15) | C8—C13—H13 | 120.1 |
C8—P1—C14 | 102.95 (15) | C12—C13—H13 | 120.1 |
C2—P1—Ir1 | 109.39 (10) | C15—C14—C19 | 118.7 (3) |
C8—P1—Ir1 | 118.73 (11) | C15—C14—P1 | 124.9 (3) |
C14—P1—Ir1 | 110.90 (11) | C19—C14—P1 | 116.5 (3) |
C3—C2—C7 | 119.5 (3) | C14—C15—C16 | 120.1 (4) |
C3—C2—P1 | 119.3 (3) | C14—C15—H15 | 119.9 |
C7—C2—P1 | 121.1 (3) | C16—C15—H15 | 119.9 |
C4—C3—C2 | 119.8 (3) | C17—C16—C15 | 120.7 (4) |
C4—C3—H3 | 120.1 | C17—C16—H16 | 119.6 |
C2—C3—H3 | 120.1 | C15—C16—H16 | 119.6 |
C5—C4—C3 | 120.7 (4) | C18—C17—C16 | 119.5 (4) |
C5—C4—H4 | 119.7 | C18—C17—H17 | 120.2 |
C3—C4—H4 | 119.7 | C16—C17—H17 | 120.2 |
C6—C5—C4 | 119.7 (3) | C17—C18—C19 | 120.1 (4) |
C6—C5—H5 | 120.2 | C17—C18—H18 | 120.0 |
C4—C5—H5 | 120.2 | C19—C18—H18 | 120.0 |
C5—C6—C7 | 120.9 (4) | C14—C19—C18 | 120.9 (4) |
C5—C6—H6 | 119.5 | C14—C19—H19 | 119.6 |
C7—C6—H6 | 119.5 | C18—C19—H19 | 119.6 |
C6—C7—C2 | 119.4 (3) | F1—B1—F1i | 84.1 (17) |
C6—C7—H7 | 120.3 | F1—B1—F2i | 114.8 (7) |
C2—C7—H7 | 120.3 | F1—B1—F2 | 136.5 (16) |
C13—C8—C9 | 119.5 (3) | F2i—B1—F2 | 79.1 (16) |
C13—C8—P1 | 125.2 (2) | F2'i—B1—F2' | 142.8 (19) |
C9—C8—P1 | 115.3 (3) | F2'i—B1—F1' | 104.1 (4) |
C10—C9—C8 | 119.8 (4) | F2'—B1—F1' | 88.7 (10) |
C10—C9—H9 | 120.1 | F1'—B1—F1'i | 139.5 (15) |
C1—Ir1—P1—C2 | −103.38 (16) | P1—C8—C9—C10 | −178.1 (3) |
C1i—Ir1—P1—C2 | −5.44 (16) | C8—C9—C10—C11 | −1.9 (6) |
Cl1—Ir1—P1—C2 | 78.16 (12) | C9—C10—C11—C12 | 0.1 (6) |
Cl1i—Ir1—P1—C2 | 172.92 (12) | C10—C11—C12—C13 | 1.2 (6) |
C1—Ir1—P1—C8 | 135.65 (16) | C9—C8—C13—C12 | −1.2 (5) |
C1i—Ir1—P1—C8 | −126.41 (16) | P1—C8—C13—C12 | 179.5 (3) |
Cl1—Ir1—P1—C8 | −42.82 (12) | C11—C12—C13—C8 | −0.7 (5) |
Cl1i—Ir1—P1—C8 | 51.95 (12) | C2—P1—C14—C15 | 11.7 (4) |
C1—Ir1—P1—C14 | 16.78 (17) | C8—P1—C14—C15 | 123.3 (3) |
C1i—Ir1—P1—C14 | 114.72 (17) | Ir1—P1—C14—C15 | −108.7 (3) |
Cl1—Ir1—P1—C14 | −161.68 (13) | C2—P1—C14—C19 | −169.2 (3) |
Cl1i—Ir1—P1—C14 | −66.92 (12) | C8—P1—C14—C19 | −57.6 (3) |
C8—P1—C2—C3 | −164.7 (3) | Ir1—P1—C14—C19 | 70.4 (3) |
C14—P1—C2—C3 | −54.8 (3) | C19—C14—C15—C16 | −1.0 (6) |
Ir1—P1—C2—C3 | 66.5 (3) | P1—C14—C15—C16 | 178.0 (3) |
C8—P1—C2—C7 | 20.5 (3) | C14—C15—C16—C17 | 0.1 (7) |
C14—P1—C2—C7 | 130.4 (3) | C15—C16—C17—C18 | 0.3 (6) |
Ir1—P1—C2—C7 | −108.3 (3) | C16—C17—C18—C19 | 0.2 (6) |
C7—C2—C3—C4 | −3.4 (5) | C15—C14—C19—C18 | 1.5 (5) |
P1—C2—C3—C4 | −178.3 (3) | P1—C14—C19—C18 | −177.6 (3) |
C2—C3—C4—C5 | 1.5 (6) | C17—C18—C19—C14 | −1.2 (6) |
C3—C4—C5—C6 | 1.2 (6) | F2i—B1—F1—F1i | 139.1 (12) |
C4—C5—C6—C7 | −2.0 (6) | F2—B1—F1—F1i | −120.3 (7) |
C5—C6—C7—C2 | 0.1 (6) | F2'i—B1—F1—F1i | 107.2 (13) |
C3—C2—C7—C6 | 2.6 (5) | F2'—B1—F1—F1i | −98.2 (5) |
P1—C2—C7—C6 | 177.4 (3) | F1'—B1—F1—F1i | −151.3 (17) |
C2—P1—C8—C13 | −128.6 (3) | F1'i—B1—F1—F1i | 14.9 (9) |
C14—P1—C8—C13 | 117.3 (3) | F1—B1—F2—F2i | −114.7 (8) |
Ir1—P1—C8—C13 | −5.7 (3) | F1i—B1—F2—F2i | 136.4 (13) |
C2—P1—C8—C9 | 52.0 (3) | F2'i—B1—F2—F2i | 14.8 (8) |
C14—P1—C8—C9 | −62.1 (3) | F2'—B1—F2—F2i | −154.5 (16) |
Ir1—P1—C8—C9 | 175.0 (2) | F1'—B1—F2—F2i | −98.8 (7) |
C13—C8—C9—C10 | 2.5 (5) | F1'i—B1—F2—F2i | 107.6 (11) |
Symmetry code: (i) −x+1, −y+1, z. |
Experimental details
Crystal data | |
Chemical formula | [IrCl2(C18H15P)2(CO)2]BF4 |
Mr | 930.47 |
Crystal system, space group | Orthorhombic, P21212 |
Temperature (K) | 150 |
a, b, c (Å) | 11.2488 (5), 14.6091 (7), 10.6711 (5) |
V (Å3) | 1753.63 (14) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 4.11 |
Crystal size (mm) | 0.20 × 0.16 × 0.11 |
Data collection | |
Diffractometer | CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.504, 0.637 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15288, 4021, 3873 |
Rint | 0.044 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.022, 0.046, 0.99 |
No. of reflections | 4021 |
No. of parameters | 246 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.47, −0.50 |
Absolute structure | Flack (1983), 1721 Friedel pairs |
Absolute structure parameter | −0.015 (5) |
Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97, PLATON (Spek, 2003), WinGX (Farrugia, 1999) and enCIFer (Allen et al., 2004).
Ir1—C1 | 1.911 (4) | C1—O1 | 1.116 (4) |
Ir1—Cl1 | 2.3629 (8) | B1—F1 | 1.318 (8) |
Ir1—P1 | 2.4258 (8) | B1—F2 | 1.361 (7) |
C1—Ir1—C1i | 97.9 (2) | Cl1—Ir1—P1 | 87.52 (3) |
Cl1—Ir1—Cl1i | 94.77 (5) | O1—C1—Ir1 | 173.8 (3) |
C1—Ir1—P1 | 90.08 (9) |
Symmetry code: (i) −x+1, −y+1, z. |
Late transition metal complexes are increasingly being exploited in carbon–fluorine bond cleavages, and the resulting metal–fluoro complexes often exhibit interesting reactivities. Much research has focused on the use of nickel-containing systems (Cornin et al., 1997; Schaub & Radius, 2005), as these have been shown to exhibit remarkable chemoselectivity (Sladek et al., 2002). The viability of homogeneous rhodium-catalysed carbon–fluorine bond activation is well established (Aizenberg & Milstein, 1994; Aizenberg & Milstein, 1995), and carbon–fluorine bond scission using iridium is not unprecedented (Kulawiec et al., 1987). Theoretical studies indicate that carbon–fluorine bond activation at IrI should be facile (Su & Chu, 1997), and many examples of carbon–fluorine bond activation using other platinum group metals now exist (Braun et al., 2002; Garratt et al., 2005; Torrens, 2005). As part of our ongoing studies into low-valent metal–fluoro complexes, we wished to investigate carbon–fluorine bond activation using [Ir(COD)(PPh3)2]+[BF4]-. Herein, we report the reaction between carbonyl fluoride and [Ir(COD)(PPh3)2]+[BF4]-.
Carbonyl fluoride, on reaction at room temperature with a stirred solution of [Ir(COD)(PPh3)2]+[BF4]- in dichloromethane, generated a significant amount of precipitate. Removal of all volatiles in vacuo yielded an air-sensitive solid, and isolation and purification of this afforded the product, [IrCl2(CO)2(PPh3)2]+[BF4]-, (I). Each of the ions lies across a twofold rotation axis. The coordination environment of the iridium is essentially octahedral (Fig. 1), with two cis Cl ligands each trans to a CO ligand, so that the two phosphane ligands are trans to one another. The [BF4]- counter-ion exhibits substantial disorder. The absence of a metal-bound fluoride in (I) is surprising and suggests that, if a fluoro complex was initially formed, the fate of the metal-bound fluoride lay in halide exchange with the chlorinated solvent. NMR studies of the crude reaction mixture lends credence to this, with a number of resonances ascribed to varying degrees of solvent fluorination being observed. However, it should be stressed that no spectroscopic evidence for a metal-bound fluoride was observed; the 31P{1H} NMR spectrum of the crude reaction mixture indicated quantitative formation of (I).
Although (I) is isoelectronic and isostructural with the well known complexes [OsCl2(CO)2L2] (L = phosphane), little work involving either cationic iridium halide or hydride complexes has been reported. Indeed, (I) represents the first iridium carbonyl phosphane chloride complex to be crystallographically characterized, and is one of only a handful of charged iridium halide complexes employing both PPh3 and CO that have been isolated. Complexes similar to (I) have, however, been observed in iridium hydride chemistry; it has been reported (Malatesta et al., 1974) that reaction of [Ir(CO)3PPh3]2 with HClO4 resulted in the formation of the cation [IrH2(CO)2(PPh3)2]+, while a range of complexes of the type [IrH2L2(CO)2]+ (L = phosphane) have also been isolated (Mays et al., 1970). The formation of [IrI2(CO)2(PPh3)2]+ has been inferred (Malatesta et al., 1970), but it could not be purified. Arguably the closest crystallographically characterized comparators to (I) are [IrCl2(CO)(PEt3)2(SOCl)] (Blake et al., 1992), and the isostructural complex [OsCl2(CO)2(PEt3)2] (Clark et al., 1999). As expected, the metal–phosphane bond lengths in [IrCl2(CO)(PEt3)2(SOCl)] [2.4257 (8) Å] and [OsCl2(CO)2(PEt3)2] [2.4048 (11) Å] are close to those observed in (I) [2.4258 (8) Å]. The metal–chloride bond lengths of (I) are, however, slightly shorter [2.3629 (8) Å] than those of the isoelectronic complex [OsCl2(CO)2(PEt3)2] [2.444 (1) Å], indicating a slightly stronger metal–chloride interaction in (I), as expected from the cationic nature of the complex.