Oxidative addition to U(V)-U(V) dimers: Facile routes to uranium(VI) bis(imido) complexes

Article abstract of DOI:10.1021/ic901581r

The ability of dimeric bis(imido) uranium(V) complexes with the general formula [U(N^tBu)₂(Y)(^tBu₂bpy)] ₂ (Y = I (1), SPh (2); ^tBu₂bpy = 4,4'-di-tert-butyl-2,2'-bipyridyl) to beha

Full text of DOI:10.1021/ic901581r

Supplemental information to accompany, Oxidative Addition to U(V)-U(V) Dimers:
Facile Routes to Uranium(VI) Bis(imido) Complexes
Liam P. Spencer, Ping Yang, Brian L. Scott, Enrique R. Batista, James M. Boncella*
Los Alamos National Laboratory, MS J514, Los Alamos NM, 87545
Email: boncella@lanl.gov
Contents:
Page
Crystallographic data for [U(NtBu)2(SPh)(tBu2bpy)]2 (2)
Crystallographic data for U(NtBu)2(Cl)(I)(tBu2bpy) (4)
S2
S3
S4
S5
S6
S7
Crystallographic data for U(NtBu)2(SePh)(I)(tBu2bpy) (8)
Crystallographic data for [(U(NtBu)2(I)(tBu2bpy))2(µ-O)] (13)
Crystallographic data for [U(NtBu)2(I)(tBu2bpy)]2(µ-η2: η2-Se4) (17)
1H NMR studies of the equilbrium between U(NtBu)2(SePh)(I)(tBu2bpy)
(8) and U(NtBu)2(SePh)2(tBu2bpy) (9) / U(NtBu)2(I)2(tBu2bpy) (3)
Comparison of theoretical and experimental bond parameters in
[(U(NtBu)2(I)(tBu2bpy))2(µ-E)] (E =O(13); S(14); Se(15) and model
complexes [U(NtBu)2(I)(bpy)]2(µ-E)] (13’-15’)
S8
S9
Geometry Optimization for [U(NtBu)2(I)(bpy)]2(µ-E)] (13’)
Geometry Optimization for [U(NtBu)2(I)(bpy)]2(µ-S)] (14’)
Geometry Optimization for [U(NtBu)2(I)(bpy)]2(µ-Se)] (15’)
S1

Table S1. Crystal data and structure refinement for [U(NtBu)2(SPh)(tBu2bpy)]2 (2).
Identification code
Empirical formula
Formula weight
Temperature
apx682a
C66 H98 Cl4 N8 S2 U2
1685.50
120(1) K
Wavelength
0.71073 Å
Crystal system
Space group
Monoclinic
P 21/c
Unit cell dimensions
a = 12.359(2) Å
b = 26.174(4) Å
c = 11.2726(19) Å
α= 90°.
β= 98.713(2)°.
γ = 90°.
3
Volume
3604.3(11) Å
2
Z
3
Density (calculated)
Absorption coefficient
F(000)
1.553 Mg/m
-1
4.736 mm
1668
3
Crystal size
0.16 x 0.14 x 0.14 mm
1.84 to 28.32°.
Theta range for data collection
Index ranges
-16<=h<=16, -34<=k<=33, -14<=l<=14
40293
Reflections collected
Independent reflections
Completeness to theta = 25.00°
Absorption correction
Max. and min. transmission
Refinement method
Data / restraints / parameters
8498 [R(int) = 0.0688]
100.0 %
Semi-empirical from equivalents
0.5569 and 0.5179
2
Full-matrix least-squares on F
8498 / 0 / 380
2
Goodness-of-fit on F
1.038
Final R indices [I>2sigma(I)]
R indices (all data)
R1 = 0.0367, wR2 = 0.0769
R1 = 0.0613, wR2 = 0.0857
-3
Largest diff. peak and hole
1.425 and -1.121 e.Å
S2

Table S2. Crystal data and structure refinement for U(NtBu)2(Cl)(I)(tBu2bpy) (4).
Identification code
Empirical formula
Formula weight
Temperature
apx594
C26 H42 Cl I N4 U
811.02
293(2) K
Wavelength
0.71073 Å
Crystal system
Space group
monoclinic
C 2/c
Unit cell dimensions
a = 19.096(8) Å
b = 14.268(6) Å
c = 22.477(9) Å
α = 90°.
β = 95.921(5)°.
γ = 90°.
3
Volume
6092(4) Å
8
Z
3
Density (calculated)
Absorption coefficient
F(000)
1.769 Mg/m
-1
6.450 mm
3104
3
Crystal size
0.14 x 0.14 x 0.12 mm
1.79 to 26.10°.
Theta range for data collection
Index ranges
-23<=h<=23, -17<=k<=15, -27<=l<=19
Reflections collected
Independent reflections
Completeness to theta = 25.00°
Max. and min. transmission
Refinement method
Data / restraints / parameters
15452
6020 [R(int) = 0.0574]
99.7 %
0.5116 and 0.4654
2
Full-matrix least-squares on F
6020 / 0 / 310
2
Goodness-of-fit on F
1.043
Final R indices [I>2sigma(I)]
R indices (all data)
R1 = 0.0474, wR2 = 0.1118
R1 = 0.0718, wR2 = 0.1216
-3
Largest diff. peak and hole
2.155 and -1.593 e.Å
S3

Table S3. Crystal data and structure refinement for U(NtBu)2(SePh)(I)(tBu2bpy) (8).
Identification code
Empirical formula
Formula weight
Temperature
apx659s
C39 H57 I N4 Se U
1025.78
120(1) K
Wavelength
0.71073 Å
Crystal system
Space group
Monoclinic
P 21/n
Unit cell dimensions
a = 13.928(3) Å
b = 14.961(3) Å
c = 20.327(4) Å
α= 90°.
β= 96.152(2)°.
γ = 90°.
3
Volume
4211.3(15) Å
4
Z
3
Density (calculated)
Absorption coefficient
F(000)
1.618 Mg/m
-1
5.481 mm
1992
3
Crystal size
0.20 x 0.10 x 0.08 mm
1.87 to 25.17°.
Theta range for data collection
Index ranges
-16<=h<=16, -17<=k<=17, -24<=l<=24
39036
Reflections collected
Independent reflections
Completeness to theta = 25.00°
Absorption correction
Max. and min. transmission
Refinement method
Data / restraints / parameters
7505 [R(int) = 0.0805]
99.9 %
Semi-empirical from equivalents
0.6682 and 0.4070
2
Full-matrix least-squares on F
7505 / 231 / 505
2
Goodness-of-fit on F
1.009
Final R indices [I>2sigma(I)]
R indices (all data)
R1 = 0.0464, wR2 = 0.1166
R1 = 0.0709, wR2 = 0.1252
-3
Largest diff. peak and hole
0.986 and -1.454 e.Å
S4

Table S4. Crystal data and structure refinement for [(U(NtBu)2(I)(tBu2bpy))2(µ-O)] (13).
Identification code
Empirical formula
Formula weight
Temperature
apx685s
C58 H98 I2 N8 O U2
1653.30
120(1) K
Wavelength
0.71073 Å
Crystal system
Space group
Monoclinic
P 21/c
Unit cell dimensions
a = 13.114(2) Å
b = 19.609(3) Å
c = 26.552(4) Å
α= 90°.
β= 101.454(2)°.
γ = 90°.
3
Volume
6691.8(19) Å
4
Z
3
Density (calculated)
Absorption coefficient
F(000)
1.641 Mg/m
-1
5.797 mm
3200
3
Crystal size
0.20 x 0.14 x 0.08 mm
1.88 to 25.22°.
Theta range for data collection
Index ranges
-15<=h<=15, -23<=k<=23, -31<=l<=31
62450
Reflections collected
Independent reflections
Completeness to theta = 25.00°
Absorption correction
Max. and min. transmission
Refinement method
Data / restraints / parameters
12016 [R(int) = 0.0945]
99.9 %
Semi-empirical from equivalents
0.6542 and 0.3902
2
Full-matrix least-squares on F
12016 / 36 / 535
2
Goodness-of-fit on F
0.799
Final R indices [I>2sigma(I)]
R indices (all data)
R1 = 0.0508, wR2 = 0.1388
R1 = 0.1009, wR2 = 0.1648
-3
Largest diff. peak and hole
1.549 and -1.439 e.Å
S5

Table S5. Crystal data and structure refinement for [U(NtBu)2(I)(tBu2bpy)]2(ꢀ-η2:η2-Se4)
(17).
Identification code
Empirical formula
Formula weight
Temperature
apx674
C80 H116 I2 N8 Se4 U2
2235.51
120(1) K
Wavelength
0.71073 Å
Crystal system
Space group
monoclinic
P 21/n
Unit cell dimensions
a = 12.291(3) Å
b = 21.472(5) Å
c = 16.935(4) Å
α= 90°.
β= 103.485(2)°.
γ = 90°.
3
Volume
4346.4(16) Å
2
Z
3
Density (calculated)
Absorption coefficient
F(000)
1.708 Mg/m
-1
6.150 mm
2156
3
Crystal size
0.28 x 0.10 x 0.10 mm
1.86 to 25.16°.
Theta range for data collection
Index ranges
-14<=h<=14, -25<=k<=25, -20<=l<=20
40322
Reflections collected
Independent reflections
Completeness to theta = 25.00°
Max. and min. transmission
Refinement method
Data / restraints / parameters
7754 [R(int) = 0.0635]
100.0 %
0.5783 and 0.2778
2
Full-matrix least-squares on F
7754 / 31 / 440
2
Goodness-of-fit on F
1.053
Final R indices [I>2sigma(I)]
R indices (all data)
R1 = 0.0353, wR2 = 0.0836
R1 = 0.0536, wR2 = 0.0913
-3
Largest diff. peak and hole
2.748 and -1.626 e.Å
S6

1
Figure S1. H NMR studies of the equilbrium between U(NtBu)2(SePh)(I)(tBu2bpy) (8)
(δ 10.67, 11.01 o-Hbpy) and U(NtBu)2(SePh)2(tBu2bpy) (9 (δ 10.90 o-Hbpy)) /
U(NtBu)2(I)2(tBu2bpy) (3) (δ 10.80 o-Hbpy).a
(a)
(b)
a (a) before the addition of U(NtBu)2(I)2(tBu2bpy) (3); (b) represents after the addition of
U(NtBu)2(I)2(tBu2bpy) (3).
S7

Table S2. Comparison of theoretical and experimental bond parameters in
[(U(NtBu)2(I)(tBu2bpy)]2(µ-E)] (E =O(13); S(14); Se(15) and model complexes
[U(NtBu)2(I)(bpy)]2(µ-E)] (13’-15’).
U-Nbpy
(avg)
U-I
(avg)
U-O
(avg)
Nimido-U-Nimido
(avg)
U-Nimido (avg)
U-O-U
1.869
2.532
3.112 2.104
173.3
165.4
Expt.
1.879
2.620
3.144 2.128
173.8
165.1
Theoretical
S8

Table S3. Geometry Optimization for [U(NtBu)2(I)(bpy)]2(µ-O)] (13’) expressed as
Cartesian coordinates.
U
2.095624 0.345559 0.073284
U -2.100294 -0.333056 0.057331
I -2.521084 -3.192599 1.284430
I
N
N
2.405061 3.380109 0.854761
4.623094 -0.280328 -0.253429
2.678981 -2.116293 -0.590813
N -4.592945 0.383645 -0.354217
N -2.361948 0.508599 1.709354
N
N
2.384791 -0.267047 1.824206
2.261363 0.798188 -1.745640
N -2.304468 -1.061740 -1.669997
N -2.544429 2.071888 -0.870143
C -5.558830 -0.514610 -0.114780
H -5.226438 -1.466787 0.293693
C
3.950602 -2.535276 -0.790400
C -3.795739 2.551823 -1.056803
C -4.915701 1.592333 -0.859708
C -6.247123 1.908452 -1.166339
H -6.502213 2.867772 -1.601411
C -7.247827 0.973447 -0.919587
C
5.019310 -1.511449 -0.640159
C -6.903576 -0.262431 -0.373597
H -7.651171 -1.019771 -0.161425
C
H
4.222603 -3.871293 -1.105527
5.240752 -4.207724 -1.261452
C -2.565921 1.169926 3.001755
C
C
C
H
C
H
7.319310 -0.780169 -0.696236
2.551183 -0.796146 3.183338
5.534722 0.686866 -0.081305
5.143746 1.653962 0.229619
1.673471 -2.996434 -0.685097
0.678335 -2.606422 -0.500483
C -1.498594 2.902021 -0.989008
H -0.520198 2.470530 -0.809176
C
H
6.374072 -1.786362 -0.874076
6.694337 -2.770661 -1.195127
C -4.008271 3.898342 -1.376300
H -5.013134 4.284185 -1.503439
C
H
C
H
C
1.871689 -4.342314 -0.994050
1.017330 -5.008094 -1.053347
6.897201 0.484300 -0.290038
7.598182 1.298266 -0.137072
3.173405 -4.783262 -1.209059
S9

C -2.450680 -1.880208 -2.877749
C
H
H
H
2.097869 0.265460 4.202776
1.043052 0.515822 4.054553
2.682808 1.183924 4.093878
2.222501 -0.109606 5.226620
C -1.634955 4.254382 -1.300262
H -0.751060 4.880961 -1.357607
C -2.917266 4.756332 -1.502515
C
H
H
H
1.709143 -2.076337 3.333452
0.649367 -1.878372 3.147517
1.811442 -2.487513 4.345734
2.038831 -2.841163 2.621388
C -1.629696 2.388905 3.102512
H -1.868786 3.126313 2.328543
H -0.583599 2.095415 2.972126
H -1.734055 2.876233 4.080318
C -4.036195 1.626306 3.083075
H -4.260443 2.337862 2.280425
H -4.237509 2.118731 4.042729
H -4.712408 0.770496 2.983206
C -1.310986 -2.915090 -2.932009
H -1.354875 -3.562576 -2.050194
H -0.337539 -2.413457 -2.954881
H -1.397143 -3.540606 -3.829531
C
H
H
H
C
4.042601 -1.119591 3.401758
4.388241 -1.867617 2.678835
4.206327 -1.519604 4.410321
4.655094 -0.218842 3.286295
2.379943 1.157353 -3.158112
C -2.397318 -0.964135 -4.114615
H -3.189788 -0.208667 -4.069030
H -2.532102 -1.547373 -5.034494
H -1.435895 -0.445317 -4.175652
C -3.808720 -2.610609 -2.829533
H -3.867945 -3.246249 -1.940889
H -3.939661 -3.238952 -3.719672
H -4.633595 -1.889788 -2.798039
C
H
H
H
0.991286 1.545960 -3.702791
0.273167 0.740804 -3.524836
1.036639 1.747233 -4.780702
0.621011 2.448572 -3.202973
C -2.262589 0.162967 4.123792
H -2.884805 -0.730963 4.018466
H -2.450482 0.612977 5.107238
H -1.216218 -0.155030 4.083690
C
3.350136 2.342926 -3.305284
S10

H
H
H
C
H
H
H
O
H
H
4.349067 2.074357 -2.943655
3.004192 3.202914 -2.723055
3.437273 2.643196 -4.357727
2.927209 -0.064329 -3.924494
2.255797 -0.922300 -3.817682
3.909547 -0.348699 -3.530108
3.037147 0.160499 -4.992818
0.013356 -0.070088 -0.020094
3.378048 -5.822443 -1.449043
8.371080 -0.984163 -0.875050
H -8.282219 1.208270 -1.153312
H -3.073679 5.805144 -1.737598
S11

Table S4. Geometry Optimization for [U(NtBu)2(I)(bpy)]2(µ-S)] (14’) expressed as
Cartesian coordinates.
U
2.651967 0.300850 0.032306
U -2.646004 -0.294020 0.036285
I -3.280049 -3.329031 0.441228
I
N
N
3.258446 3.350253 0.351585
5.101220 -0.586627 -0.149026
3.003274 -2.283083 -0.229467
N -5.095848 0.590178 -0.160809
N -2.873610 0.058089 1.843068
N
N
2.882098 0.010432 1.850630
2.799318 0.453090 -1.812759
N -2.795203 -0.513506 -1.802316
N -2.993756 2.278484 -0.308374
C -6.092853 -0.303795 -0.090475
H -5.791958 -1.336887 0.066953
C
4.234903 -2.833996 -0.331307
C -4.225221 2.830090 -0.407710
C -5.381739 1.895945 -0.352864
C -6.710300 2.324067 -0.487960
H -6.942329 3.369394 -0.651192
C -7.743331 1.394023 -0.415798
C
5.389151 -1.895559 -0.314302
C -7.434277 0.050876 -0.210455
H -8.205402 -0.709277 -0.145938
C
H
4.395020 -4.221623 -0.436634
5.381863 -4.662173 -0.511267
C -2.887173 0.208605 3.302586
C
C
C
H
C
H
7.747806 -1.387135 -0.418784
2.905681 -0.095035 3.314481
6.095399 0.312265 -0.111892
5.792119 1.347810 0.024016
1.924056 -3.082417 -0.226591
0.967077 -2.578338 -0.135481
C -1.912596 3.074646 -0.341348
H -0.955540 2.570703 -0.250653
C
H
6.717360 -2.322246 -0.456710
6.951033 -3.370211 -0.599580
C -4.383127 4.215151 -0.546393
H -5.369664 4.656597 -0.619844
C
H
C
H
C
2.009866 -4.470086 -0.329743
1.103397 -5.065968 -0.320034
7.436578 -0.040579 -0.240192
8.205805 0.723312 -0.202780
3.272378 -5.046318 -0.437062
S12

C -2.762635 -0.922897 -3.212643
C
H
H
H
2.092123 1.066854 3.912527
1.058345 1.028171 3.555336
2.521430 2.028394 3.614241
2.087235 1.005932 5.008058
C -1.996254 4.459510 -0.477864
H -1.087992 5.052453 -0.494997
C -3.258574 5.036526 -0.582360
C
H
H
H
2.291665 -1.447920 3.719400
1.264480 -1.527559 3.349877
2.279275 -1.553647 4.811289
2.872060 -2.278372 3.300996
C -2.252215 1.563885 3.664344
H -2.827171 2.390525 3.230928
H -1.228679 1.620553 3.281230
H -2.225862 1.698163 4.752833
C -4.352153 0.159701 3.777109
H -4.934186 0.967007 3.317259
H -4.407282 0.273555 4.866972
H -4.810108 -0.797042 3.504930
C -1.611636 -1.924725 -3.418807
H -1.776357 -2.822218 -2.814080
H -0.660309 -1.475713 -3.116780
H -1.545530 -2.219213 -4.473804
C
H
H
H
C
4.371787 -0.010537 3.780077
4.964102 -0.822899 3.343288
4.433062 -0.089425 4.872697
4.814066 0.944104 3.476484
2.741718 0.768982 -3.245197
C -2.543917 0.331010 -4.080035
H -3.357122 1.050931 -3.932904
H -2.512278 0.061759 -5.143238
H -1.600016 0.819918 -3.819000
C -4.108493 -1.586146 -3.562969
H -4.281552 -2.457645 -2.923612
H -4.111412 -1.913659 -4.610176
H -4.936533 -0.881503 -3.423494
C
H
H
H
1.584960 1.753929 -3.496213
0.641430 1.328354 -3.139900
1.494258 1.972903 -4.567661
1.762960 2.692360 -2.961086
C -2.087359 -0.947503 3.929645
H -2.527633 -1.910698 3.653021
H -2.082920 -0.860417 5.023413
H -1.052579 -0.929592 3.573049
C
4.080354 1.409478 -3.659758
S13

H
H
H
C
H
H
H
H
H
4.912168 0.716863 -3.485544
4.261433 2.321743 -3.082694
4.067123 1.666910 -4.726342
2.512720 -0.540091 -4.023327
1.572615 -1.009189 -3.716682
3.328115 -1.248124 -3.836205
2.467854 -0.344185 -5.101896
3.388531 -6.123363 -0.516584
8.779227 -1.709539 -0.528278
H -8.774957 1.717692 -0.519481
H -3.373210 6.111577 -0.687264
S
0.003338 0.005938 0.036054
S14

Table S5. Geometry Optimization for [U(NtBu)2(I)(bpy)]2(µ-Se)] (15’) expressed as
Cartesian coordinates.
U
2.722606 0.175841 0.042976
U -2.766596 -0.348579 0.034890
I -4.066049 -3.137599 0.561277
I
N
N
2.816694 3.295017 0.397171
5.302210 -0.195110 -0.159024
3.579167 -2.274442 -0.295530
N -5.029148 0.932968 -0.268067
N -2.930421 0.090532 1.822442
N
N
3.005860 -0.095837 1.853421
2.795089 0.360552 -1.801505
N -2.890347 -0.619731 -1.792871
N -2.660255 2.230326 -0.375088
C -6.169368 0.226452 -0.241726
H -6.060301 -0.836757 -0.043464
C
4.895668 -2.564674 -0.410808
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S15

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S16

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S17