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C5H5-Fe-C5H4Br |
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Bromine |
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Nuclear
Quadrupole Coupling Constants |
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in Bromoferrocene
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Calculation of the Br nqcc tensors in bromoferrocene was made on a partial ro
structure derived by Drouin et al. [1], and on an ropt structure given by PBE1PBE/6-31G(df,pd) optimization.
These are compared with experimental nqcc tensors [1] in Table 1.
Structure parameters are given in Table 2, rotational constanst in
Table 3.
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In Table 1, subscripts a,b,c refer to the
principal axes of the inertia tensor; x,y,z to the principal axes
of the nqcc tensor. The nqcc y-axis is chosen coincident with the
inertia c-axis, these are perpendicular to the molecular symmetry plane.
Ø (degrees) is the angle between its subscripted
parameters. ETA = (Xxx - Xyy)/Xzz. |
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RMS is the root mean square difference
between calculated and experimental diagonal nqcc's (percentage of the
average of the magnitudes of the experimental nqcc's). RSD is the
calibration residual standard deviation for the B1LYP/TZV(3df,3p) model
for calculation of the bromine nqcc's.
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Table 1. Bromine
nqcc's in Bromoferrocene (MHz). Calculation was made the partial ro and PBE1PBE/6-31G(df,pd) ropt structures.
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Calc / ro
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Calc / ropt |
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Expt. [1] |
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79Br |
Xaa |
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256.66
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264.96
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267.16(3)
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Xbb |
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38.40
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20.77
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21.49(4) |
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Xcc |
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295.06
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285.73
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288.66(4) |
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|Xab| |
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429.80
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411.33
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409.81(4)
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RMS |
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12.07 (6.27 %)
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2.15 (1.12 %)
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RSD |
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1.58 (0.39 %)
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1.58 (0.39 %) |
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Xxx |
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295.90
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286.20
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283.49
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Xyy |
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295.06
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285.73
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288.66(4)
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Xzz |
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590.96
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571.93
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572.15
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ETA |
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0.0014
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0.0008
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0.011
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Øz,a |
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37.88
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36.73
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Øa,CBr |
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37.18
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Øz,CBr |
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0.45
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81Br |
Xaa |
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216.94
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223.68
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225.40(6)
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Xbb |
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21.57
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15.04
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15.65(4)
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Xcc |
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246.51
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238.72
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241.05(4) |
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|Xab| |
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358.44
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342.96
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341.62(4)
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RMS |
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9.92 (6.17 %)
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1.71 (1.06 %)
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RSD |
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1.38 (0.40 %)
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1.38 (0.40 %) |
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Table 2. Bromoferrocene partial ro structure parameters (Å and degrees). This structure, and the PBE1PBE/6-31G(df,pd) ropt structure are given here in Z-matrix format.
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Fe-Cp is perpendicular distance between Fe and C5 plane.
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Fe-Cp
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1.63(2)
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| Fe-CpBr is perpendicular distance between Fe and C5Br plane. |
Fe-CpBr
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1.67(3)
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C-C distances assumed all equal.
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C-C
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1.433(1)
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C-H = 1.08 Å assumed.
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C-Br
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1.875(11)
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| C-H bond makes angle C5-H with the C5-plane. |
C5-H
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4.6
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Table 3. Bromoferrocene. Rotational constants (MHz). Normal species.
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ropt structure
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Expt [1]
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A
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1295.09
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1272.110(1)
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B
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534.20
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516.1125(2)
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C
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456.64
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441.3775(2)
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[1] B.J.Drouin, T.G.Lavaty, P.A.Cassak, and S.G.Kukolich, J.Chem.Phys. 107(17),6541(1997).
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Chloroferrocene
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Table of Contents |
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Molecules/Bromine |
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bromoferrocene.html |
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Last
Modified 24 Nov 2011 |
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