The title compound, [RhBr(C18H15P)2(CO)], can be characterized as a rhodium(I) Vaska-type compound based only on the spectroscopic [νKBr(CO), 31P] data. A low-temperature X-ray crystallographic analysis shows that the compound possesses a crystallographically imposed centre of symmetry with a statistically disordered Br atom and CO group. The essentially different occupancies for the Br atom and the CO group [0.283 (2) and 0.717 (2), respectively] suggest that the compound exists as a mixture of rhodium(0), rhodium(I) and rhodium(II) complexes.
Supporting information
CCDC reference: 608591
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.002 Å
- Disorder in main residue
- R factor = 0.018
- wR factor = 0.047
- Data-to-parameter ratio = 19.5
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 1.04
PLAT077_ALERT_4_C Unitcell contains non-integer number of atoms .. ?
PLAT213_ALERT_2_C Atom Br has ADP max/min Ratio ............. 4.00 prolat
PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 3.18 Ratio
PLAT301_ALERT_3_C Main Residue Disorder ......................... 8.00 Perc.
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
5 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
2 ALERT type 2 Indicator that the structure model may be wrong or deficient
1 ALERT type 3 Indicator that the structure quality may be low
2 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg & Putz, 2004); software used to prepare material for publication: SHELXL97.
trans-Bromocarbonylbis(triphenylphosphine)rhodium
top
Crystal data top
[RhBr(C18H15P)2(CO)] | Z = 1 |
Mr = 712.84 | F(000) = 360.9 |
Triclinic, P1 | Dx = 1.472 Mg m−3 |
Hall symbol: -p 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.1519 (4) Å | Cell parameters from 8332 reflections |
b = 9.5797 (5) Å | θ = 2.6–28.3° |
c = 10.2796 (5) Å | µ = 1.36 mm−1 |
α = 73.040 (2)° | T = 100 K |
β = 89.016 (2)° | Plate, yellow |
γ = 69.567 (2)° | 0.37 × 0.12 × 0.07 mm |
V = 804.19 (7) Å3 | |
Data collection top
Bruker APEX 24K CCD area-detector diffractometer | 4011 independent reflections |
Radiation source: fine-focus sealed tube | 3855 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
Detector resolution: 512 x 512 pixels mm-1 | θmax = 28.3°, θmin = 2.4° |
φ and ω scans | h = −12→12 |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | k = −12→12 |
Tmin = 0.762, Tmax = 0.877 | l = −13→13 |
21423 measured reflections | |
Refinement top
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)] = 0.018 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.047 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0192P)2 + 0.4097P] where P = (Fo2 + 2Fc2)/3 |
4011 reflections | (Δ/σ)max = 0.001 |
206 parameters | Δρmax = 0.39 e Å−3 |
0 restraints | Δρmin = −0.54 e Å−3 |
Special details top
Experimental. Spectral data: 1H NMR (CDCl3, 300 MHz): 7.68 (m, 12H), 7.48 (m, 6H), 7.35 (m, 12H); 31P NMR (CDCl3, 75 MHz):
30.11 (d, 1J 133.67 Hz). IR νKBr(CO): 1969 (s) cm-1. |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds 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 > 2sigma(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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Rh | 0.5000 | 0.0000 | 0.5000 | 0.01169 (4) | |
P | 0.51567 (3) | −0.20414 (3) | 0.69633 (3) | 0.01267 (7) | |
C31 | 0.60990 (13) | −0.18920 (14) | 0.84385 (12) | 0.0150 (2) | |
C11 | 0.32540 (14) | −0.21141 (14) | 0.74499 (12) | 0.0160 (2) | |
C12 | 0.29214 (15) | −0.25401 (15) | 0.88053 (13) | 0.0177 (2) | |
H12 | 0.3682 | −0.2784 | 0.9507 | 0.021* | |
C21 | 0.62559 (16) | −0.40332 (15) | 0.69401 (13) | 0.0188 (2) | |
C32 | 0.62014 (15) | −0.04582 (16) | 0.83738 (13) | 0.0204 (2) | |
H32 | 0.5781 | 0.0393 | 0.7595 | 0.024* | |
C36 | 0.67359 (16) | −0.31624 (16) | 0.96180 (13) | 0.0215 (3) | |
H36 | 0.6684 | −0.4130 | 0.9672 | 0.026* | |
C13 | 0.14530 (16) | −0.26016 (17) | 0.91116 (14) | 0.0236 (3) | |
H13 | 0.1226 | −0.2863 | 1.0016 | 0.028* | |
C22 | 0.78850 (17) | −0.45225 (17) | 0.69448 (14) | 0.0261 (3) | |
H22 | 0.8394 | −0.3858 | 0.7017 | 0.031* | |
C14 | 0.03292 (16) | −0.22734 (19) | 0.80679 (16) | 0.0281 (3) | |
H14 | −0.0645 | −0.2332 | 0.8276 | 0.034* | |
C26 | 0.5514 (2) | −0.50360 (17) | 0.68120 (16) | 0.0311 (3) | |
H26 | 0.4431 | −0.4727 | 0.6800 | 0.037* | |
C33 | 0.69295 (17) | −0.02891 (18) | 0.94667 (15) | 0.0265 (3) | |
H33 | 0.7002 | 0.0670 | 0.9412 | 0.032* | |
C16 | 0.21037 (16) | −0.17588 (18) | 0.64093 (14) | 0.0261 (3) | |
H16 | 0.2310 | −0.1453 | 0.5502 | 0.031* | |
C25 | 0.6398 (3) | −0.6506 (2) | 0.6701 (2) | 0.0468 (5) | |
H25 | 0.5897 | −0.7169 | 0.6608 | 0.056* | |
C34 | 0.75439 (16) | −0.15451 (19) | 1.06328 (14) | 0.0267 (3) | |
H34 | 0.8022 | −0.1428 | 1.1365 | 0.032* | |
C15 | 0.06518 (17) | −0.1858 (2) | 0.67177 (16) | 0.0319 (3) | |
H15 | −0.0101 | −0.1647 | 0.6020 | 0.038* | |
C35 | 0.74476 (17) | −0.29776 (19) | 1.07107 (14) | 0.0272 (3) | |
H35 | 0.7860 | −0.3821 | 1.1497 | 0.033* | |
C23 | 0.8749 (2) | −0.5994 (2) | 0.68420 (17) | 0.0398 (4) | |
H23 | 0.9833 | −0.6311 | 0.6850 | 0.048* | |
C24 | 0.8004 (3) | −0.69856 (19) | 0.67278 (19) | 0.0477 (5) | |
H24 | 0.8584 | −0.7975 | 0.6669 | 0.057* | |
O1 | 0.2387 (5) | 0.1954 (5) | 0.5970 (5) | 0.0330 (13) | 0.717 (2) |
C1 | 0.3282 (6) | 0.1286 (5) | 0.5619 (4) | 0.0324 (8) | 0.717 (2) |
Br | 0.27493 (14) | 0.17121 (15) | 0.58152 (13) | 0.0160 (3) | 0.283 (2) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Rh | 0.01082 (7) | 0.01196 (7) | 0.01031 (6) | −0.00325 (5) | 0.00168 (4) | −0.00160 (4) |
P | 0.01220 (14) | 0.01350 (14) | 0.01164 (13) | −0.00555 (11) | 0.00082 (11) | −0.00167 (11) |
C31 | 0.0113 (5) | 0.0198 (6) | 0.0135 (5) | −0.0061 (5) | 0.0014 (4) | −0.0039 (4) |
C11 | 0.0140 (5) | 0.0169 (6) | 0.0175 (6) | −0.0075 (5) | 0.0019 (4) | −0.0034 (4) |
C12 | 0.0178 (6) | 0.0187 (6) | 0.0177 (6) | −0.0079 (5) | 0.0028 (5) | −0.0055 (5) |
C21 | 0.0237 (6) | 0.0143 (6) | 0.0148 (5) | −0.0044 (5) | 0.0000 (5) | −0.0022 (4) |
C32 | 0.0192 (6) | 0.0204 (6) | 0.0205 (6) | −0.0065 (5) | −0.0015 (5) | −0.0054 (5) |
C36 | 0.0205 (6) | 0.0241 (7) | 0.0175 (6) | −0.0094 (5) | −0.0007 (5) | −0.0010 (5) |
C13 | 0.0231 (7) | 0.0286 (7) | 0.0233 (6) | −0.0134 (6) | 0.0102 (5) | −0.0097 (5) |
C22 | 0.0232 (7) | 0.0268 (7) | 0.0228 (7) | 0.0000 (6) | −0.0028 (5) | −0.0104 (6) |
C14 | 0.0176 (6) | 0.0378 (8) | 0.0352 (8) | −0.0154 (6) | 0.0086 (6) | −0.0139 (6) |
C26 | 0.0401 (9) | 0.0203 (7) | 0.0345 (8) | −0.0144 (6) | 0.0013 (7) | −0.0060 (6) |
C33 | 0.0242 (7) | 0.0301 (7) | 0.0296 (7) | −0.0096 (6) | −0.0005 (6) | −0.0157 (6) |
C16 | 0.0208 (6) | 0.0401 (8) | 0.0180 (6) | −0.0155 (6) | 0.0005 (5) | −0.0039 (6) |
C25 | 0.0733 (14) | 0.0198 (8) | 0.0478 (11) | −0.0166 (9) | −0.0032 (9) | −0.0110 (7) |
C34 | 0.0199 (6) | 0.0435 (9) | 0.0200 (6) | −0.0099 (6) | 0.0007 (5) | −0.0161 (6) |
C15 | 0.0193 (7) | 0.0493 (10) | 0.0291 (7) | −0.0168 (7) | −0.0019 (6) | −0.0091 (7) |
C35 | 0.0235 (7) | 0.0369 (8) | 0.0148 (6) | −0.0087 (6) | −0.0029 (5) | −0.0011 (5) |
C23 | 0.0368 (9) | 0.0366 (9) | 0.0285 (8) | 0.0139 (7) | −0.0101 (7) | −0.0166 (7) |
C24 | 0.0688 (13) | 0.0198 (8) | 0.0358 (9) | 0.0104 (8) | −0.0140 (9) | −0.0124 (7) |
O1 | 0.036 (2) | 0.0299 (18) | 0.0182 (14) | 0.0023 (15) | 0.0091 (12) | −0.0026 (9) |
C1 | 0.039 (2) | 0.0307 (19) | 0.0196 (14) | −0.0132 (16) | −0.0007 (14) | 0.0041 (12) |
Br | 0.0115 (6) | 0.0167 (5) | 0.0128 (4) | 0.0034 (5) | 0.0079 (4) | −0.0051 (3) |
Geometric parameters (Å, º) top
Rh—C1 | 1.861 (6) | C13—H13 | 0.9300 |
Rh—C1i | 1.861 (6) | C22—C23 | 1.389 (2) |
Rh—P | 2.3302 (3) | C22—H22 | 0.9300 |
Rh—Pi | 2.3302 (3) | C14—C15 | 1.385 (2) |
Rh—Bri | 2.4533 (13) | C14—H14 | 0.9300 |
Rh—Br | 2.4533 (13) | C26—C25 | 1.395 (2) |
P—C11 | 1.8225 (12) | C26—H26 | 0.9300 |
P—C31 | 1.8225 (12) | C33—C34 | 1.382 (2) |
P—C21 | 1.8273 (13) | C33—H33 | 0.9300 |
C31—C32 | 1.3914 (18) | C16—C15 | 1.3898 (19) |
C31—C36 | 1.3997 (17) | C16—H16 | 0.9300 |
C11—C12 | 1.3932 (17) | C25—C24 | 1.376 (3) |
C11—C16 | 1.3944 (18) | C25—H25 | 0.9300 |
C12—C13 | 1.3923 (18) | C34—C35 | 1.385 (2) |
C12—H12 | 0.9300 | C34—H34 | 0.9300 |
C21—C26 | 1.3902 (19) | C15—H15 | 0.9300 |
C21—C22 | 1.3977 (19) | C35—H35 | 0.9300 |
C32—C33 | 1.3928 (18) | C23—C24 | 1.379 (3) |
C32—H32 | 0.9300 | C23—H23 | 0.9300 |
C36—C35 | 1.3925 (19) | C24—H24 | 0.9300 |
C36—H36 | 0.9300 | O1—C1 | 0.985 (7) |
C13—C14 | 1.387 (2) | C1—Br | 0.592 (6) |
| | | |
C1—Rh—C1i | 180.0 (2) | C14—C13—C12 | 120.02 (12) |
C1—Rh—P | 88.75 (11) | C14—C13—H13 | 120.0 |
C1i—Rh—P | 91.25 (10) | C12—C13—H13 | 120.0 |
C1—Rh—Pi | 91.25 (11) | C23—C22—C21 | 120.53 (15) |
C1i—Rh—Pi | 88.75 (10) | C23—C22—H22 | 119.7 |
P—Rh—Pi | 180.0 | C21—C22—H22 | 119.7 |
C1—Rh—Bri | 179.45 (11) | C15—C14—C13 | 120.25 (12) |
C1i—Rh—Bri | 0.55 (11) | C15—C14—H14 | 119.9 |
P—Rh—Bri | 90.95 (3) | C13—C14—H14 | 119.9 |
Pi—Rh—Bri | 89.05 (3) | C21—C26—C25 | 119.90 (16) |
C1—Rh—Br | 0.55 (11) | C21—C26—H26 | 120.1 |
C1i—Rh—Br | 179.45 (11) | C25—C26—H26 | 120.1 |
P—Rh—Br | 89.05 (3) | C34—C33—C32 | 120.10 (14) |
Pi—Rh—Br | 90.95 (3) | C34—C33—H33 | 120.0 |
Bri—Rh—Br | 180.000 (1) | C32—C33—H33 | 120.0 |
C11—P—C31 | 105.88 (5) | C15—C16—C11 | 120.53 (13) |
C11—P—C21 | 103.26 (6) | C15—C16—H16 | 119.7 |
C31—P—C21 | 103.64 (6) | C11—C16—H16 | 119.7 |
C11—P—Rh | 113.54 (4) | C24—C25—C26 | 120.78 (17) |
C31—P—Rh | 111.77 (4) | C24—C25—H25 | 119.6 |
C21—P—Rh | 117.56 (4) | C26—C25—H25 | 119.6 |
C32—C31—C36 | 119.10 (12) | C33—C34—C35 | 119.98 (13) |
C32—C31—P | 118.27 (9) | C33—C34—H34 | 120.0 |
C36—C31—P | 122.62 (10) | C35—C34—H34 | 120.0 |
C12—C11—C16 | 119.24 (11) | C14—C15—C16 | 119.77 (13) |
C12—C11—P | 122.89 (9) | C14—C15—H15 | 120.1 |
C16—C11—P | 117.86 (10) | C16—C15—H15 | 120.1 |
C13—C12—C11 | 120.15 (12) | C34—C35—C36 | 120.35 (13) |
C13—C12—H12 | 119.9 | C34—C35—H35 | 119.8 |
C11—C12—H12 | 119.9 | C36—C35—H35 | 119.8 |
C26—C21—C22 | 118.86 (13) | C24—C23—C22 | 120.15 (17) |
C26—C21—P | 122.00 (11) | C24—C23—H23 | 119.9 |
C22—C21—P | 118.95 (10) | C22—C23—H23 | 119.9 |
C31—C32—C33 | 120.48 (13) | C25—C24—C23 | 119.76 (15) |
C31—C32—H32 | 119.8 | C25—C24—H24 | 120.1 |
C33—C32—H32 | 119.8 | C23—C24—H24 | 120.1 |
C35—C36—C31 | 119.98 (13) | Br—C1—Rh | 177.7 (5) |
C35—C36—H36 | 120.0 | O1—C1—Rh | 178.6 (5) |
C31—C36—H36 | 120.0 | | |
| | | |
C1—Rh—P—C11 | 40.51 (12) | C11—P—C21—C22 | −163.99 (10) |
C1i—Rh—P—C11 | −139.49 (12) | C31—P—C21—C22 | −53.71 (11) |
Bri—Rh—P—C11 | −139.03 (5) | Rh—P—C21—C22 | 70.15 (11) |
Br—Rh—P—C11 | 40.97 (5) | C36—C31—C32—C33 | 0.08 (19) |
C1—Rh—P—C31 | −79.19 (12) | P—C31—C32—C33 | −179.12 (10) |
C1i—Rh—P—C31 | 100.81 (12) | C32—C31—C36—C35 | 0.56 (19) |
Bri—Rh—P—C31 | 101.27 (5) | P—C31—C36—C35 | 179.73 (10) |
Br—Rh—P—C31 | −78.73 (5) | C11—C12—C13—C14 | 1.5 (2) |
C1—Rh—P—C21 | 161.15 (12) | C26—C21—C22—C23 | −0.9 (2) |
C1i—Rh—P—C21 | −18.85 (12) | P—C21—C22—C23 | −175.98 (12) |
Bri—Rh—P—C21 | −18.39 (6) | C12—C13—C14—C15 | −1.1 (2) |
Br—Rh—P—C21 | 161.61 (6) | C22—C21—C26—C25 | 0.5 (2) |
C11—P—C31—C32 | −106.11 (10) | P—C21—C26—C25 | 175.42 (13) |
C21—P—C31—C32 | 145.56 (10) | C31—C32—C33—C34 | −0.6 (2) |
Rh—P—C31—C32 | 18.00 (11) | C12—C11—C16—C15 | −1.3 (2) |
C11—P—C31—C36 | 74.72 (11) | P—C11—C16—C15 | 177.26 (12) |
C21—P—C31—C36 | −33.61 (12) | C21—C26—C25—C24 | 0.5 (3) |
Rh—P—C31—C36 | −161.18 (9) | C32—C33—C34—C35 | 0.5 (2) |
C31—P—C11—C12 | −20.45 (12) | C13—C14—C15—C16 | −0.5 (2) |
C21—P—C11—C12 | 88.14 (11) | C11—C16—C15—C14 | 1.7 (2) |
Rh—P—C11—C12 | −143.45 (9) | C33—C34—C35—C36 | 0.1 (2) |
C31—P—C11—C16 | 161.03 (11) | C31—C36—C35—C34 | −0.7 (2) |
C21—P—C11—C16 | −90.37 (12) | C21—C22—C23—C24 | 0.3 (2) |
Rh—P—C11—C16 | 38.04 (12) | C26—C25—C24—C23 | −1.1 (3) |
C16—C11—C12—C13 | −0.29 (19) | C22—C23—C24—C25 | 0.7 (3) |
P—C11—C12—C13 | −178.79 (10) | O1—C1—Br—Rh | 146 (13) |
C11—P—C21—C26 | 21.06 (13) | P—Rh—Br—C1 | −57 (11) |
C31—P—C21—C26 | 131.34 (12) | Pi—Rh—Br—C1 | 123 (11) |
Rh—P—C21—C26 | −104.80 (11) | | |
Symmetry code: (i) −x+1, −y, −z+1. |
Comparative X-ray data for [Rh(X)CO(PPh3)2] complexes topX | Rh—X | Rh—C | C═O | Disorder | Space group |
Cla | 2.356 | 1.847 | 1.126 | N | P21/c |
Clb | 2.405 | 1.987 | 0.739 | Y | P1 |
Clc | 2.371 | 1.810 | 1.143 | N | P21/n |
Cld | 2.381 | 1.759 | 1.143 | Y | P-1 |
Cle | 2.383 | 1.761 | 1.150 | Y | Pbca |
Brf | 2.453 | 1.862 | 0.984 | Y | P-1 |
Ig | 2.684 | 1.807 | 1.140 | N | P21/n |
Notes: (a) (Muir & Ibers, 1969);
(b) (Del Pra et al., 1979);
(c) (Ceriotti et al., 1983);
(d) (Chen et al., 1991);
(e) (Dunbar & Haefner, 1992);
(f) this work;
(g) (Basson et al., 1990). |