metal-organic compounds
[1,2-Bis(dimethylphosphino)ethane]carbonyl(η5-cyclopentadienyl)iron(II) diphenylphosphinoylborate
aSchool of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS, England, and bDepartment of Chemistry, University of Toronto, Toronto, Ontario, Canada M5S 3H6
*Correspondence e-mail: alough@chem.utoronto.ca
In the title compound, [Fe(C5H5)(C6H16P2)(CO)](C12H13BOP), the FeII ion adopts a three-legged piano-stool geometry, with Fe⋯Cg = 1.721 (5)Å (Cg = the centroid defined by the C atoms of the cyclopentadienyl ring). The 1,2-bis(dimethylphosphino)ethane (dmpe) ligand chelates to form a five-membered C2P2Fe ring which is in a pseudo-half-chair conformation. In the associations of one cation and two anions are formed via weak intermolecular C—H⋯O hydrogen bonds, giving rise to R42(9) rings.
Related literature
For related literature, see: Jaska et al. (2003, 2005); Kuckmann et al. (2007); Paciello et al. (1990). For background on graph-set theory, see: Bernstein et al. (1995).
Experimental
Crystal data
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Refinement
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Data collection: COLLECT (Nonius, 2002); cell DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXTL (Sheldrick, 2001); molecular graphics: PLATON (Spek, 2003) and SHELXTL; software used to prepare material for publication: SHELXTL
Supporting information
10.1107/S1600536807068651/hb2681sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536807068651/hb2681Isup2.hkl
The complex CpFe(CO)2PPh2.BH3 (200 mg, 0.532 mmol) was dissolved in 1.8 ml THF in a round bottom Schlenk flask. This yellow solution turned orange upon addition of dmpe (0.150 ml, 0.899 mmol). After 8 days of stirring at 293 K, orange precipitate was observed in the solution. The solution was filter cannulated into a new flask and then the volatile components of the reaction mixture were removed in vacuo overnight. The product was purified by
with a column of celite (0.5 cm × 1.5 cm) supported on glass wool with hexanes (4 ml), Et2O (5 ml) and then THF (4 ml). The product in THF afforded pale yellow needles of (II) due to adventitious air.All hydrogen atoms bonded to C were placed in calculated positions with C—H = 0.95–1.00 Å and refined as riding with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(Cmethyl). The H atoms bonded to B1 were refined independently with isotropic displacement parameters.
Data collection: Collect (Nonius, 1997-2002); cell
DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXTL (Sheldrick, 2001); molecular graphics: PLATON (Spek, 2003) and SHELXTL (Sheldrick, 2001); software used to prepare material for publication: SHELXTL (Sheldrick, 2001).[Fe(C5H5)(C6H16P2)(CO)](C12H13BOP) | Z = 2 |
Mr = 514.08 | F(000) = 540 |
Triclinic, P1 | Dx = 1.341 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.0244 (5) Å | Cell parameters from 8558 reflections |
b = 11.4671 (4) Å | θ = 2.6–25.0° |
c = 14.0568 (7) Å | µ = 0.80 mm−1 |
α = 67.491 (3)° | T = 150 K |
β = 81.155 (2)° | Cut needle, pale yellow |
γ = 71.497 (3)° | 0.20 × 0.14 × 0.12 mm |
V = 1273.50 (11) Å3 |
Nonius KappaCCD diffractometer | 4217 independent reflections |
Radiation source: fine-focus sealed tube | 2935 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.091 |
Detector resolution: 9 pixels mm-1 | θmax = 25.0°, θmin = 2.6° |
ϕ scans and ω scans with κ offsets | h = −10→10 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | k = −12→13 |
Tmin = 0.521, Tmax = 0.943 | l = −16→16 |
8558 measured reflections |
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)] = 0.058 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.176 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0844P)2 + 1.3773P] where P = (Fo2 + 2Fc2)/3 |
4217 reflections | (Δ/σ)max = 0.002 |
296 parameters | Δρmax = 0.81 e Å−3 |
0 restraints | Δρmin = −0.79 e Å−3 |
[Fe(C5H5)(C6H16P2)(CO)](C12H13BOP) | γ = 71.497 (3)° |
Mr = 514.08 | V = 1273.50 (11) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.0244 (5) Å | Mo Kα radiation |
b = 11.4671 (4) Å | µ = 0.80 mm−1 |
c = 14.0568 (7) Å | T = 150 K |
α = 67.491 (3)° | 0.20 × 0.14 × 0.12 mm |
β = 81.155 (2)° |
Nonius KappaCCD diffractometer | 4217 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 2935 reflections with I > 2σ(I) |
Tmin = 0.521, Tmax = 0.943 | Rint = 0.091 |
8558 measured reflections |
R[F2 > 2σ(F2)] = 0.058 | 0 restraints |
wR(F2) = 0.176 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.81 e Å−3 |
4217 reflections | Δρmin = −0.79 e Å−3 |
296 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 | ||
Fe1 | 0.22249 (8) | 0.31967 (6) | 0.79005 (5) | 0.0227 (2) | |
P1 | −0.03606 (15) | 0.38455 (12) | 0.78938 (10) | 0.0256 (3) | |
P2 | 0.20337 (15) | 0.11946 (11) | 0.82546 (10) | 0.0231 (3) | |
O1 | 0.2462 (5) | 0.3727 (4) | 0.5707 (3) | 0.0444 (10) | |
C1 | 0.4180 (6) | 0.3862 (5) | 0.7772 (4) | 0.0339 (13) | |
H1A | 0.4862 | 0.4108 | 0.7139 | 0.041* | |
C2 | 0.4403 (6) | 0.2587 (5) | 0.8551 (4) | 0.0294 (12) | |
H2A | 0.5270 | 0.1779 | 0.8568 | 0.035* | |
C3 | 0.3203 (6) | 0.2692 (5) | 0.9321 (4) | 0.0319 (13) | |
H3A | 0.3063 | 0.1965 | 0.9974 | 0.038* | |
C4 | 0.2271 (6) | 0.4001 (5) | 0.9012 (4) | 0.0305 (12) | |
H4A | 0.1336 | 0.4357 | 0.9409 | 0.037* | |
C5 | 0.2834 (6) | 0.4729 (5) | 0.8063 (4) | 0.0326 (13) | |
H5A | 0.2400 | 0.5691 | 0.7674 | 0.039* | |
C6 | −0.1017 (6) | 0.2512 (5) | 0.7849 (4) | 0.0328 (12) | |
H6A | −0.2134 | 0.2631 | 0.8071 | 0.039* | |
H6B | −0.0893 | 0.2506 | 0.7138 | 0.039* | |
C7 | −0.0015 (6) | 0.1229 (5) | 0.8573 (4) | 0.0301 (12) | |
H7A | −0.0212 | 0.0471 | 0.8492 | 0.036* | |
H7B | −0.0275 | 0.1172 | 0.9297 | 0.036* | |
C8 | −0.1254 (7) | 0.5297 (5) | 0.6827 (4) | 0.0397 (14) | |
H8A | −0.2394 | 0.5477 | 0.6902 | 0.060* | |
H8B | −0.0891 | 0.5149 | 0.6178 | 0.060* | |
H8C | −0.0961 | 0.6052 | 0.6824 | 0.060* | |
C9 | −0.1446 (6) | 0.4183 (6) | 0.9003 (4) | 0.0372 (13) | |
H9A | −0.2544 | 0.4233 | 0.8977 | 0.056* | |
H9B | −0.1377 | 0.5022 | 0.8996 | 0.056* | |
H9C | −0.1003 | 0.3476 | 0.9636 | 0.056* | |
C10 | 0.2542 (6) | 0.0595 (5) | 0.7200 (4) | 0.0337 (13) | |
H10A | 0.2284 | −0.0237 | 0.7398 | 0.051* | |
H10B | 0.3665 | 0.0453 | 0.7031 | 0.051* | |
H10C | 0.1952 | 0.1244 | 0.6596 | 0.051* | |
C11 | 0.3108 (6) | −0.0181 (5) | 0.9308 (4) | 0.0318 (12) | |
H11A | 0.2859 | −0.0984 | 0.9380 | 0.048* | |
H11B | 0.2812 | −0.0001 | 0.9950 | 0.048* | |
H11C | 0.4233 | −0.0300 | 0.9163 | 0.048* | |
C12 | 0.2342 (6) | 0.3517 (4) | 0.6586 (4) | 0.0275 (12) | |
P3 | 0.21995 (16) | 0.08074 (12) | 0.22685 (10) | 0.0265 (3) | |
O2 | 0.3092 (5) | 0.0325 (4) | 0.1455 (3) | 0.0482 (11) | |
C13 | 0.3424 (6) | 0.1487 (4) | 0.2728 (4) | 0.0246 (11) | |
C14 | 0.4211 (6) | 0.2322 (5) | 0.1986 (4) | 0.0287 (12) | |
H14A | 0.4080 | 0.2534 | 0.1276 | 0.034* | |
C15 | 0.5184 (6) | 0.2844 (5) | 0.2277 (4) | 0.0346 (13) | |
H15A | 0.5714 | 0.3412 | 0.1765 | 0.042* | |
C16 | 0.5383 (6) | 0.2541 (5) | 0.3308 (4) | 0.0332 (12) | |
H16A | 0.6064 | 0.2886 | 0.3505 | 0.040* | |
C17 | 0.4598 (6) | 0.1742 (5) | 0.4046 (4) | 0.0328 (13) | |
H17A | 0.4721 | 0.1550 | 0.4754 | 0.039* | |
C18 | 0.3619 (6) | 0.1208 (5) | 0.3767 (4) | 0.0283 (12) | |
H18A | 0.3082 | 0.0653 | 0.4285 | 0.034* | |
C20 | 0.2031 (6) | −0.0630 (4) | 0.3411 (4) | 0.0249 (11) | |
C21 | 0.0648 (6) | −0.0653 (5) | 0.4012 (4) | 0.0303 (12) | |
H21A | −0.0229 | 0.0107 | 0.3858 | 0.036* | |
C22 | 0.0560 (7) | −0.1787 (5) | 0.4833 (4) | 0.0355 (13) | |
H22A | −0.0384 | −0.1800 | 0.5238 | 0.043* | |
C23 | 0.1819 (7) | −0.2897 (5) | 0.5070 (4) | 0.0348 (13) | |
H23A | 0.1741 | −0.3672 | 0.5631 | 0.042* | |
C24 | 0.3195 (6) | −0.2878 (5) | 0.4489 (4) | 0.0351 (13) | |
H24A | 0.4072 | −0.3637 | 0.4659 | 0.042* | |
C25 | 0.3308 (6) | −0.1761 (5) | 0.3662 (4) | 0.0310 (12) | |
H25A | 0.4257 | −0.1761 | 0.3262 | 0.037* | |
B1 | 0.0223 (8) | 0.2119 (6) | 0.1944 (5) | 0.0338 (14) | |
H1 | 0.045 (6) | 0.298 (5) | 0.132 (4) | 0.030 (13)* | |
H2 | −0.037 (7) | 0.166 (6) | 0.160 (5) | 0.062 (18)* | |
H3 | −0.020 (6) | 0.244 (5) | 0.265 (4) | 0.043 (15)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.0241 (4) | 0.0196 (4) | 0.0260 (4) | −0.0091 (3) | −0.0030 (3) | −0.0068 (3) |
P1 | 0.0240 (7) | 0.0230 (7) | 0.0301 (7) | −0.0048 (5) | −0.0049 (6) | −0.0097 (6) |
P2 | 0.0233 (7) | 0.0193 (7) | 0.0280 (7) | −0.0083 (5) | −0.0021 (5) | −0.0077 (5) |
O1 | 0.061 (3) | 0.040 (2) | 0.027 (2) | −0.012 (2) | −0.0033 (19) | −0.0081 (17) |
C1 | 0.033 (3) | 0.037 (3) | 0.037 (3) | −0.023 (3) | −0.003 (2) | −0.007 (2) |
C2 | 0.030 (3) | 0.024 (3) | 0.037 (3) | −0.008 (2) | −0.011 (2) | −0.009 (2) |
C3 | 0.045 (3) | 0.032 (3) | 0.029 (3) | −0.024 (3) | −0.007 (3) | −0.008 (2) |
C4 | 0.034 (3) | 0.036 (3) | 0.035 (3) | −0.015 (2) | 0.001 (2) | −0.024 (2) |
C5 | 0.034 (3) | 0.026 (3) | 0.046 (3) | −0.015 (2) | −0.007 (3) | −0.014 (2) |
C6 | 0.018 (3) | 0.039 (3) | 0.052 (3) | −0.012 (2) | −0.002 (2) | −0.025 (3) |
C7 | 0.025 (3) | 0.028 (3) | 0.045 (3) | −0.013 (2) | 0.001 (2) | −0.017 (2) |
C8 | 0.034 (3) | 0.033 (3) | 0.038 (3) | 0.004 (2) | −0.011 (3) | −0.006 (2) |
C9 | 0.029 (3) | 0.050 (3) | 0.038 (3) | −0.011 (3) | 0.005 (2) | −0.024 (3) |
C10 | 0.040 (3) | 0.024 (3) | 0.039 (3) | −0.010 (2) | −0.003 (3) | −0.013 (2) |
C11 | 0.037 (3) | 0.021 (3) | 0.034 (3) | −0.009 (2) | −0.005 (2) | −0.004 (2) |
C12 | 0.031 (3) | 0.017 (3) | 0.034 (3) | −0.008 (2) | −0.007 (2) | −0.005 (2) |
P3 | 0.0302 (8) | 0.0211 (7) | 0.0302 (7) | −0.0117 (6) | −0.0063 (6) | −0.0059 (5) |
O2 | 0.058 (3) | 0.043 (2) | 0.048 (3) | −0.021 (2) | 0.001 (2) | −0.0176 (19) |
C13 | 0.027 (3) | 0.017 (3) | 0.028 (3) | −0.003 (2) | −0.006 (2) | −0.007 (2) |
C14 | 0.032 (3) | 0.025 (3) | 0.029 (3) | −0.012 (2) | −0.004 (2) | −0.006 (2) |
C15 | 0.036 (3) | 0.030 (3) | 0.042 (3) | −0.017 (2) | −0.002 (3) | −0.011 (2) |
C16 | 0.034 (3) | 0.030 (3) | 0.044 (3) | −0.016 (2) | −0.007 (3) | −0.014 (2) |
C17 | 0.037 (3) | 0.027 (3) | 0.035 (3) | −0.007 (2) | −0.012 (2) | −0.009 (2) |
C18 | 0.029 (3) | 0.021 (3) | 0.032 (3) | −0.009 (2) | 0.002 (2) | −0.007 (2) |
C20 | 0.028 (3) | 0.027 (3) | 0.028 (3) | −0.015 (2) | −0.008 (2) | −0.011 (2) |
C21 | 0.025 (3) | 0.029 (3) | 0.038 (3) | −0.008 (2) | −0.003 (2) | −0.012 (2) |
C22 | 0.032 (3) | 0.037 (3) | 0.038 (3) | −0.015 (3) | 0.004 (2) | −0.012 (2) |
C23 | 0.048 (4) | 0.030 (3) | 0.027 (3) | −0.021 (3) | 0.002 (3) | −0.005 (2) |
C24 | 0.036 (3) | 0.028 (3) | 0.038 (3) | −0.005 (2) | −0.011 (3) | −0.008 (2) |
C25 | 0.031 (3) | 0.029 (3) | 0.033 (3) | −0.008 (2) | 0.000 (2) | −0.012 (2) |
B1 | 0.034 (4) | 0.029 (3) | 0.039 (4) | −0.010 (3) | −0.007 (3) | −0.010 (3) |
Fe1—C12 | 1.733 (5) | C10—H10A | 0.9800 |
Fe1—P1 | 2.2129 (15) | C10—H10B | 0.9800 |
Fe1—P2 | 2.2133 (13) | C10—H10C | 0.9800 |
Fe1—C2 | 2.093 (5) | C11—H11A | 0.9800 |
Fe1—C1 | 2.093 (5) | C11—H11B | 0.9800 |
Fe1—C5 | 2.097 (5) | C11—H11C | 0.9800 |
Fe1—C3 | 2.105 (5) | P3—O2 | 1.477 (4) |
Fe1—C4 | 2.107 (5) | P3—C20 | 1.837 (5) |
P1—C8 | 1.811 (5) | P3—C13 | 1.844 (5) |
P1—C9 | 1.815 (5) | P3—B1 | 1.917 (6) |
P1—C6 | 1.831 (5) | C13—C18 | 1.396 (7) |
P2—C10 | 1.804 (5) | C13—C14 | 1.396 (7) |
P2—C11 | 1.818 (5) | C14—C15 | 1.388 (7) |
P2—C7 | 1.826 (5) | C14—H14A | 0.9500 |
O1—C12 | 1.160 (6) | C15—C16 | 1.382 (7) |
C1—C5 | 1.422 (7) | C15—H15A | 0.9500 |
C1—C2 | 1.426 (7) | C16—C17 | 1.369 (7) |
C1—H1A | 1.0000 | C16—H16A | 0.9500 |
C2—C3 | 1.418 (7) | C17—C18 | 1.394 (7) |
C2—H2A | 1.0000 | C17—H17A | 0.9500 |
C3—C4 | 1.401 (7) | C18—H18A | 0.9500 |
C3—H3A | 1.0000 | C20—C21 | 1.397 (7) |
C4—C5 | 1.394 (7) | C20—C25 | 1.401 (7) |
C4—H4A | 1.0000 | C21—C22 | 1.385 (7) |
C5—H5A | 1.0000 | C21—H21A | 0.9500 |
C6—C7 | 1.521 (7) | C22—C23 | 1.377 (8) |
C6—H6A | 0.9900 | C22—H22A | 0.9500 |
C6—H6B | 0.9900 | C23—C24 | 1.379 (7) |
C7—H7A | 0.9900 | C23—H23A | 0.9500 |
C7—H7B | 0.9900 | C24—C25 | 1.381 (7) |
C8—H8A | 0.9800 | C24—H24A | 0.9500 |
C8—H8B | 0.9800 | C25—H25A | 0.9500 |
C8—H8C | 0.9800 | B1—H1 | 1.09 (5) |
C9—H9A | 0.9800 | B1—H2 | 1.12 (6) |
C9—H9B | 0.9800 | B1—H3 | 1.15 (5) |
C9—H9C | 0.9800 | ||
C12—Fe1—C2 | 113.6 (2) | P2—C7—H7A | 110.1 |
C12—Fe1—C1 | 90.6 (2) | C6—C7—H7B | 110.1 |
C2—Fe1—C1 | 39.84 (19) | P2—C7—H7B | 110.1 |
C12—Fe1—C5 | 105.3 (2) | H7A—C7—H7B | 108.4 |
C2—Fe1—C5 | 66.7 (2) | P1—C8—H8A | 109.5 |
C1—Fe1—C5 | 39.7 (2) | P1—C8—H8B | 109.5 |
C12—Fe1—C3 | 153.0 (2) | H8A—C8—H8B | 109.5 |
C2—Fe1—C3 | 39.5 (2) | P1—C8—H8C | 109.5 |
C1—Fe1—C3 | 66.1 (2) | H8A—C8—H8C | 109.5 |
C5—Fe1—C3 | 65.9 (2) | H8B—C8—H8C | 109.5 |
C12—Fe1—C4 | 143.2 (2) | P1—C9—H9A | 109.5 |
C2—Fe1—C4 | 65.7 (2) | P1—C9—H9B | 109.5 |
C1—Fe1—C4 | 65.4 (2) | H9A—C9—H9B | 109.5 |
C5—Fe1—C4 | 38.7 (2) | P1—C9—H9C | 109.5 |
C3—Fe1—C4 | 38.9 (2) | H9A—C9—H9C | 109.5 |
C12—Fe1—P1 | 91.01 (17) | H9B—C9—H9C | 109.5 |
C2—Fe1—P1 | 155.10 (15) | P2—C10—H10A | 109.5 |
C1—Fe1—P1 | 142.78 (15) | P2—C10—H10B | 109.5 |
C5—Fe1—P1 | 104.63 (15) | H10A—C10—H10B | 109.5 |
C3—Fe1—P1 | 115.69 (16) | P2—C10—H10C | 109.5 |
C4—Fe1—P1 | 92.67 (15) | H10A—C10—H10C | 109.5 |
C12—Fe1—P2 | 91.92 (15) | H10B—C10—H10C | 109.5 |
C2—Fe1—P2 | 95.99 (14) | P2—C11—H11A | 109.5 |
C1—Fe1—P2 | 130.86 (15) | P2—C11—H11B | 109.5 |
C5—Fe1—P2 | 159.26 (15) | H11A—C11—H11B | 109.5 |
C3—Fe1—P2 | 93.58 (14) | P2—C11—H11C | 109.5 |
C4—Fe1—P2 | 124.82 (15) | H11A—C11—H11C | 109.5 |
P1—Fe1—P2 | 86.24 (5) | H11B—C11—H11C | 109.5 |
C8—P1—C9 | 102.6 (3) | O1—C12—Fe1 | 178.2 (5) |
C8—P1—C6 | 106.0 (3) | O2—P3—C20 | 107.9 (2) |
C9—P1—C6 | 103.3 (3) | O2—P3—C13 | 108.6 (2) |
C8—P1—Fe1 | 117.0 (2) | C20—P3—C13 | 101.9 (2) |
C9—P1—Fe1 | 118.65 (19) | O2—P3—B1 | 118.6 (3) |
C6—P1—Fe1 | 107.95 (17) | C20—P3—B1 | 111.6 (3) |
C10—P2—C11 | 102.7 (2) | C13—P3—B1 | 106.9 (2) |
C10—P2—C7 | 104.4 (2) | C18—C13—C14 | 118.5 (4) |
C11—P2—C7 | 104.9 (2) | C18—C13—P3 | 124.1 (4) |
C10—P2—Fe1 | 115.38 (18) | C14—C13—P3 | 117.5 (4) |
C11—P2—Fe1 | 119.88 (17) | C15—C14—C13 | 120.6 (5) |
C7—P2—Fe1 | 108.14 (16) | C15—C14—H14A | 119.7 |
C5—C1—C2 | 108.0 (5) | C13—C14—H14A | 119.7 |
C5—C1—Fe1 | 70.3 (3) | C16—C15—C14 | 120.2 (5) |
C2—C1—Fe1 | 70.1 (3) | C16—C15—H15A | 119.9 |
C5—C1—H1A | 126.0 | C14—C15—H15A | 119.9 |
C2—C1—H1A | 126.0 | C17—C16—C15 | 120.0 (5) |
Fe1—C1—H1A | 126.0 | C17—C16—H16A | 120.0 |
C3—C2—C1 | 107.2 (5) | C15—C16—H16A | 120.0 |
C3—C2—Fe1 | 70.7 (3) | C16—C17—C18 | 120.5 (5) |
C1—C2—Fe1 | 70.1 (3) | C16—C17—H17A | 119.7 |
C3—C2—H2A | 126.4 | C18—C17—H17A | 119.7 |
C1—C2—H2A | 126.4 | C17—C18—C13 | 120.2 (5) |
Fe1—C2—H2A | 126.4 | C17—C18—H18A | 119.9 |
C4—C3—C2 | 107.8 (4) | C13—C18—H18A | 119.9 |
C4—C3—Fe1 | 70.7 (3) | C21—C20—C25 | 118.8 (4) |
C2—C3—Fe1 | 69.8 (3) | C21—C20—P3 | 122.2 (4) |
C4—C3—H3A | 126.1 | C25—C20—P3 | 118.9 (4) |
C2—C3—H3A | 126.1 | C22—C21—C20 | 119.7 (5) |
Fe1—C3—H3A | 126.1 | C22—C21—H21A | 120.1 |
C5—C4—C3 | 109.6 (5) | C20—C21—H21A | 120.1 |
C5—C4—Fe1 | 70.3 (3) | C23—C22—C21 | 121.0 (5) |
C3—C4—Fe1 | 70.5 (3) | C23—C22—H22A | 119.5 |
C5—C4—H4A | 125.2 | C21—C22—H22A | 119.5 |
C3—C4—H4A | 125.2 | C22—C23—C24 | 119.6 (5) |
Fe1—C4—H4A | 125.2 | C22—C23—H23A | 120.2 |
C4—C5—C1 | 107.3 (5) | C24—C23—H23A | 120.2 |
C4—C5—Fe1 | 71.0 (3) | C23—C24—C25 | 120.5 (5) |
C1—C5—Fe1 | 70.0 (3) | C23—C24—H24A | 119.8 |
C4—C5—H5A | 126.3 | C25—C24—H24A | 119.8 |
C1—C5—H5A | 126.3 | C24—C25—C20 | 120.4 (5) |
Fe1—C5—H5A | 126.3 | C24—C25—H25A | 119.8 |
C7—C6—P1 | 107.3 (3) | C20—C25—H25A | 119.8 |
C7—C6—H6A | 110.3 | P3—B1—H1 | 107 (3) |
P1—C6—H6A | 110.3 | P3—B1—H2 | 101 (3) |
C7—C6—H6B | 110.3 | H1—B1—H2 | 107 (4) |
P1—C6—H6B | 110.3 | P3—B1—H3 | 107 (3) |
H6A—C6—H6B | 108.5 | H1—B1—H3 | 106 (4) |
C6—C7—P2 | 108.1 (3) | H2—B1—H3 | 127 (4) |
C6—C7—H7A | 110.1 |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2A···O2i | 1.00 | 2.41 | 3.389 (7) | 167 |
C3—H3A···O2ii | 1.00 | 2.20 | 3.197 (7) | 172 |
C11—H11B···O2ii | 0.98 | 2.35 | 3.281 (7) | 159 |
C11—H11C···O2i | 0.98 | 2.43 | 3.403 (7) | 171 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, y, z+1. |
Experimental details
Crystal data | |
Chemical formula | [Fe(C5H5)(C6H16P2)(CO)](C12H13BOP) |
Mr | 514.08 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 150 |
a, b, c (Å) | 9.0244 (5), 11.4671 (4), 14.0568 (7) |
α, β, γ (°) | 67.491 (3), 81.155 (2), 71.497 (3) |
V (Å3) | 1273.50 (11) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.80 |
Crystal size (mm) | 0.20 × 0.14 × 0.12 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.521, 0.943 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8558, 4217, 2935 |
Rint | 0.091 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.176, 1.05 |
No. of reflections | 4217 |
No. of parameters | 296 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.81, −0.79 |
Computer programs: Collect (Nonius, 1997-2002), DENZO-SMN (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), SHELXTL (Sheldrick, 2001), PLATON (Spek, 2003) and SHELXTL (Sheldrick, 2001), SHELXTL (Sheldrick, 2001).
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2A···O2i | 1.00 | 2.41 | 3.389 (7) | 167 |
C3—H3A···O2ii | 1.00 | 2.20 | 3.197 (7) | 172 |
C11—H11B···O2ii | 0.98 | 2.35 | 3.281 (7) | 159 |
C11—H11C···O2i | 0.98 | 2.43 | 3.403 (7) | 171 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, y, z+1. |
Acknowledgements
IM thanks the EPSRC, the University of Bristol for start-up funds, the European Union for a Marie Curie Chair and the Royal Society for a Wolfson Research Merit Award for financial support. AJL acknowledges NSERC Canada and the University of Toronto for funding.
References
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The mechanism for the metal catalyzed dehydrocoupling of phosphine-borane adducts has been studied by investigating the synthesis and reactivity of model complexes. The P—H bond oxidative addition of RPhPH-BH3 to Pt(PEt3)3 has been reported as well as the phosphine-borane ligand-exchange reaction at the Pt centre of cis-[PtH(PPh2.BH3) (depe)] (Jaska et al., 2003). Model complexes such as cis-[PtH(PPhH.BH3)(dcype)] [dcype = 1,2-bis(dicyclohexylphosphino)ethane] have been synthesized via dehydrocoupling routes involving Pt—H and P—H bonds of cis-[PtH2(dcype)] and PhPH2.BH3 respectively (Jaska et al., 2005). The reactivity of CpFe(CO)2PPh2.BH3, (I), (Kuckmann et al., 2007) [see Fig. 3] was probed as a potential model complex in the study of the mechanism of the dehydrocoupling of phosphine-borane adducts: the CO ligands might dissociate to promote a reaction with phosphine-borane adducts. Before reacting (I) with phosphine-borane adducts, dmpe (1,2-bis(dimethylphosphino)ethane) was added in excess to (I) to observe the lability of the CO ligands. When adventitious air was also introduced to this reaction in THF, the title compound, (II), (Fig. 1), was formed. A similar complex, Cp*Fe(dmpe)X (X = H, CH3 or Cl) was reported earlier (Paciello et al., 1990).
The Fe atom in (II) is bonded to a cyclopentadienyl (cp) ring with Fe···Cg = 1.721 (5)Å (Cg = the centroid of C1—C5), a carbonyl group and the bis-chelating (dimethylphosphino)ethane (dmpe) ligand (Table 1). In the crystal of (II), weak intermolecular C—H···O hydrogen bonds (Table 2) form rings with graph set assignment R24(9) (Bernstein et al., 1995) created in a three component cluster of two anions and one cation (Fig. 2).