research communications
Crystallographic characterization of (C5H4SiMe3)3U(BH4)
aLos Alamos National Laboratory, Los Alamos, New Mexico 87544, USA, and bDepartment of Chemistry, University of California, Irvine, California 92697, USA
*Correspondence e-mail: stosh@lanl.gov, wevans@uci.edu
New syntheses have been developed for the synthesis of (borohydrido-κ3H)tris[η5-(trimethylsilyl)cyclopentadienyl]uranium(IV), [U(BH4)(C8H13Si)3] or Cp′3U(BH4) (Cp′ = C5H4SiMe3) and its structure has been determined by single-crystal X-ray crystallography. This compound crystallized in the P and the structure features three η5-coordinated Cp′ rings and a κ3-coordinated (BH4)− ligand.
Keywords: crystal structure; uranium; borohydride; cyclopentadienyl compounds.
CCDC reference: 2067867
1. Chemical context
Actinide borohydrides have been of interest since the 1940s, owing to their potential volatility and applied use in vapor deposition technologies for the production of thin films (Hoekstra & Katz, 1949; Daly & Girolami, 2010). Uranium borohydride compounds are structurally interesting because the (BH4)− ligand can coordinate large electropositive cations (such as uranium) in several modes. For example, κ1, κ2, and κ3 U–(BH4) binding has previously been reported (Ephritikhine, 1997). Borohydrides can also achieve high coordination numbers with uranium, e.g. the oligomeric 14-coordinate U(BH4)4 (Bernstein et al., 1972). Although several cyclopentadienyl uranium borohydrides have been crystallographically characterized (Ephritikhine, 1997), the structure of Cp′3U(BH4) (Cp′ = C5H4SiMe3), made in 1992 (Berthet & Ephritikhine, 1992), has not been reported. Our interest in Cp′ uranium chemistry (MacDonald et al., 2013; Windorff et al., 2017) prompted us to determine the coordination mode of (BH4)− within the tris-cyclopentadienyl uranium platform using single-crystal X-ray diffraction. Toward this end, we developed new synthetic routes to the Cp′3U(BH4) compound.
The Cp′3U(BH4) compound was originally synthesized by reacting Cp′3UH with H3B-PPh3 (Berthet & Ephritikhine, 1992). Our attempts to repeat this procedure in toluene and diethyl ether solvents were unsuccessful, potentially because we were uncertain about the details of the reaction. However, we were successful in synthesizing Cp′3U(BH4) from Cp′3UH with H3B-PPh3 in hot THF solvent. We also observed Cp′3U(BH4) could be prepared in high yield (96%) by reacting Cp′3UI with NaBH4 in the presence of 15-crown-5. When this reaction was carried out in toluene at room temperature, the I− ligand was substituted by the (BH4)− anion. Another method we developed for synthesizing Cp′3U(BH4) involved reacting U(BH4)4 with KCp′ (3 equiv.) in diethyl ether. This reaction, where (BH4)− was substituted by (Cp′)−, also proceeded in high yield (89%). X-ray quality crystals of Cp′3U(BH4) formed at 253 K overnight from diethyl ether solutions.
Of our two synthetic routes, we preferred making Cp′3U(BH4) from Cp′3UI over U(BH4)4 because the U(BH4)4 starting material was more challenging to isolate in a chemically pure form. Another interesting comparison between the two synthetic methods involved the substitution chemistry. The (Cp′)− anion displaced (BH4)− from U(BH4)4 and (BH4)− displaced I− in Cp′3UI. Hence, we qualitatively concluded that the stability of the U—X bond for molecular compounds dissolved in organic solvents was largest for (Cp′)−, intermediate for (BH4)−, and lowest for I−. The generality of this conclusion is limited, and we acknowledge the solubility of the other reaction products (such as NaI) might significantly influence the substitution chemistry on uranium.
2. Structural commentary
Single crystal X-ray data from Cp′3U(BH4) were refined in the triclinic P with one crystallographically unique molecule in the see Fig. 1. The data are of high quality, and electron-density difference peaks consistent with the location and geometry of bridging hydrides were located from a difference-Fourier map with U—H distances of 2.35 (5), 2.35 (5), and 2.36 (5) Å. Although the uncertainty associated with the U—H bonds is relatively high, they are consistent with previously reported bond lengths for actinide(IV) hydride interactions (Ephritikhine, 1997; Daly et al., 2010). Significantly lower uncertainty is associated with the U—B distance at 2.568 (4) Å, which is similar to two of the three U—B distances in [U(BH4)3(DME)]2(μ-O) (DME = 1,2-dimethoxyethane), 2.574 (6), 2.584 (6), and 2.635 (7) Å (Daly et al., 2012). The U—B distance in (C5H5)3U(BH4) was reported to be 2.48 Å (Zanella et al., 1988), although disorder in that structure prevented a full solution from being obtained. Theoretical calculations on (C5H5)3U(BH4) in the gas phase and in solution predicted U—B distances of 2.533 and 2.557 Å (Elkechai et al., 2009), which are also consistent with our data. Other (C5R5)2U(BH4)2 structures showed similar U—B distances of 2.56 (1) Å for [C5H3(SiMe3)2]2U(BH4)2 (Blake et al., 1995), 2.58 (3) Å in (C5Me5)2U(BH4)2 (Gradoz et al., 1994, Marsh et al., 2002), and 2.553 (1) Å in (PC4Me4)2U(BH4)2 (Baudry et al., 1990).
The uranium–(Cp′ centroid) distances in Cp′3U(BH4) range from 2.458–2.500 Å and average 2.48 (2) Å (uncertainty reported as the standard deviation from the mean at 1σ). These uranium–(Cp′ centroid) distances compare well with the 2.473 Å analogous metric in Cp′3UCl (Windorff et al., 2017) and other Cp′3UX structures (see Table 1) with average U–(Cp′ centroid) distances of 2.478 (3) Å in Cp′3UI (Windorff et al., 2017), 2.484 (4) Å in Cp′3U(η1-CH=CH2) (Schock et al., 1988) and 2.478 (7) Å in Cp′3U[Si(SiMe3)3] (Réant et al., 2020). The 113.9 (6)° average of (Cp′ centroid)—U—(Cp′ centroid) angles in Cp′3U(BH4) is more acute than the 117.0° angle in Cp′3UCl and other Cp′3UX structures, where the average (Cp′ centroid)—U—(Cp′ centroid) angles were reported as 117 (1)° in Cp′3UI, 112 (2)° in Cp′3U(η1-CH=CH2), and 118.7 (4)° in Cp′3U[Si(SiMe3)3]. The more acute (Cp′ centroid)—U—(Cp′ centroid) angles are complemented by a more obtuse average (Cp′ centroid)—U—B angle of 104.4 (4)° in Cp′3U(BH4), likely due to the close proximity of the (BH4)1− ligand compared with (Cp′ centroid)—U—X angles of 100.0° in Cp′3UCl, 100 (2)° in Cp′3UI, 98 (3)° in Cp′3U(η1-CH=CH2), and 96.7 (9)° in Cp′3U[Si(SiMe3)3], see Table 1.
An unusual feature of the Cp′3U(BH4) structure is that all three of the trimethylsilyl groups are oriented in a single direction towards the (BH4)− unit. This orientation has not been observed in other Cp′3U(anion) and Cp′3U(μ-dianion)UCp′3 structures, which are shown in Figs. 2–12. The closest comparison is with the Cp′3UCl structure (Windorff et al., 2017), where all three trimethylsilyl groups are oriented towards the Cl− unit, but twisted down and away from the chloride towards the meridian. The Cp′3UI (Windorff et al., 2017) and Cp′3U(η1-CH=CH2) (Schock et al., 1988) complexes have one trimethylsilyl group pointed away from the anionic ligand. The Cp′3U[Si(SiMe3)3] complex (Réant et al., 2020) represents the opposite extreme where all of the trimethylsilyl groups are oriented away from the [Si(SiMe3)3]1− unit. Since Cp′3U(BH4) has the smallest mono-anion of the Cp′3U(anion) complexes and the correspondingly smallest (Cp′ centroid)—U—(Cp′ centroid), and the largest (Cp′ centroid)—U—X angles, the orientation of the could occur due to steric factors. However, it is also possible that some dispersion forces between the (BH4)− and the trimethylsilyl groups could contribute to the orientation (Liptrot et al., 2016). It is interesting to note that in the Cp′3ThX series where X = Cl (Réant et al., 2020), Br (Windorff et al., 2017), and CH3 (Wedal et al., 2019), all three trimethylsilyl groups are oriented towards the anion, but twisted down and away from the anion towards the meridian as in Cp′3UCl.
3. Supramolecular features
There are no major supramolecular features to report. The molecules pack in an alternating 180° rotation from one another within the
and stack `head to tail' between the unit cells.4. Database survey
A search using the Cambridge Structural Database (Version 5.41, March 2020; Groom et al., 2016) for borohydride structures containing η5-aromatic five-membered rings bound to uranium showed two classes of complexes. There were the uranium(IV) piano-stool complexes: (C5H5)U(BH4)3 (DEKVEU and DEKVEU10; Baudry et al., 1985, 1989); (C5Me5)U(BH4)(SPSMe) (JOJTIM; Arliguie et al., 2008), where SPSMe = PC5H-3,5-Ph,-2,6-(P(S)Ph2)-1-Me, a λ4-phosphinine with two lateral phosphinosulfide groups, and the tetramethylphosphol (PC4Me4) compound (PC4Me4)(C8H8)U(BH4)(THF) (MOBVEE; Cendrowski-Guillaume et al., 2002). There were also uranium(IV) metallocene structures, (Ring)2U(BH4)2, where Ring = C5H5 (CPURBH; Zanella et al., 1977), C5H3(SiMe3)2 (ZEYZOS; Blake et al., 1995), C5Me5 (WIFFOG and WIFFOG01; Gradoz et al., 1994; Marsh et al., 2002), C9H7 (VASVUG, C9H7 = indenide; Rebizant et al., 1989) and PC4Me4 (KIJBEK, PC4Me4 = tetramethylphosphol; Baudry et al., 1990). The macrocyclic trans-calix[2]benzene[2]pyrrolide (L) complex [LU(BH4)][B(C6F5)4] was also in the database (CUJMEB; Arnold et al., 2015). This last compound features two η5-bound NC4H2R2 ligands. Also in the database were a few examples of uranium(III) borohydrides, such as the mono borohydride [(PC4Me4)2U(BH4)]2 (YEZJES; Gradoz et al., 1994) and the mixed piano stool [Na(THF)6][(C5Me5)U(BH4)3]2 (VAXMUC; Ryan et al., 1989)] complexes.
There are also three dimeric uranium(IV) complexes with Cp′− ligands, all of the form (Cp′3U)2(μ-X) where X = O2− (SOSXON; Berthet et al., 1991), (pyrazine)2−, (N2C4H4)2− (EYERIJ; Mehdoui et al., 2004), and CCO2− (PIKFAT; Tsoureas & Cloke, 2018). There is also the tetrametallic (Cp′3U)4(μ-L) (PIKDUL; Tsoureas & Cloke, 2018) where L is a complex organic structure containing a central cyclobutene-1,3-dione ring.
5. Spectroscopic Features
The fully defined Cp′3U(BH4) compound was also characterized by 1H, 11B{1H}, 13C{1H}, and 29Si{1H} multi-nuclear NMR spectroscopy. It was of particular interest to examine the 29Si{1H} spectrum for comparison with previous studies of silicon-containing paramagnetic uranium complexes (Windorff & Evans, 2014). The 1H NMR spectrum in C7D8 was in good agreement with the literature (Berthet & Ephritikhine, 1992). 11B{1H}, 13C{1H}, and 29Si{1H} spectra were also obtained in both C7D8 and C6D6, as well as different field strengths, 500 vs 600 MHz for 1H, to see if any significant solvent or field effects were present. Since the spectra were not dependent on solvent or field strength, only the spectra obtained in C6D6 in a 600 MHz field will be discussed here. See Section 6 for full details.
In general, the resonances attributable to the Cp′− ligands are sharp (ν1/2 < 50 Hz) and paramagnetically shifted over a range of δ 9.6 to −22.6 ppm, in the 1H NMR spectrum, and a 29Si{1H} resonance at δ −57.4 ppm was observed, typical of other tetravalent uranium complexes (Windorff & Evans, 2014). The resonances attributable to the (BH4)− unit showed considerably more shifting and broadening, resonating at δ −59.5 (ν1/2 = 300 Hz) and 79.6 (ν1/2 = 240 Hz) in the 1H and 11B{1H} spectra, respectively. Since the (BH4)− ligand exhibited a single 1H NMR resonance whereas two distinct hydride environments are present in the solid state, it appears that the complex is fluxional in solution. This is in line with previous studies (Ephritikhine, 1997).
6. Synthesis and crystallization
6.1. General considerations
All manipulations and syntheses described below were conducted with the rigorous exclusion of air and water using glovebox techniques under an argon atmosphere. Solvents (THF, Et2O, toluene, hexane, and pentane) were sparged with UHP argon (Praxair) and dried by passage through columns containing a copper(II) oxide oxygen scavenger (Q-5) and molecular sieves prior to use or stirred over sodium benzophenone ketyl, briefly exposed to vacuum several times to degas and distilled under vacuum. All ethereal solvents were stored over activated 4 Å molecular sieves. Deuterated solvents (Cambridge Isotopes) used for nuclear magnetic resonance (NMR) spectroscopy were dried over sodium benzophenone ketyl, degassed by three freeze-pump-thaw cycles, and distilled under vacuum before use. The 1H, 11B{1H}, 13C{1H} and 29Si{1H} NMR spectra were recorded on a GN 500, Cryo 500 or Bruker Avance 600 spectrometer operating at 500.2 MHz, 160.1 MHz, 125.8 MHz, and 99.1 MHz for the 500 MHz spectrometers, respectively, and 600.1 MHz, 192.6 MHz, 150.9 MHz and 119.2 MHz for the 600 MHz spectrometer, respectively, at 298 K unless otherwise stated. The 1H and 13C{1H} NMR spectra were referenced internally to solvent resonances, 11B and 29Si{1H} NMR spectra were referenced externally to BF3(Et2O) and SiMe4, respectively, the 29Si{1H} spectra were acquired using the INEPT pulse sequence. The 15-crown-5 (Aldrich) reagent was dried over activated molecular sieves and degassed by three freeze–pump–thaw cycles before use. The NaBH4 (Aldrich) reagent was placed under vacuum (10 −3 Torr) for 12 h before use. The following compounds were prepared following literature procedures: KCp′ (Peterson et al., 2013), U(BH4)4 (Schlesinger & Brown, 1953), Cp′3UI (Windorff et al., 2017).
6.2. Cp′3U(BH4) from Cp′3UI, NaBH4 and 15-crown-5
Solid NaBH4 (15 mg, 0.40 mmol) was added to a C7D8 (toluene-d8, 0.6 mL) solution of Cp′3UI (37 mg, 0.048 mmol) in a J-Young NMR tube, an excess of 15-crown-5 (1 drop) was added and the tube was sealed and removed from the glovebox and vortexed (30 s). The NaBH4 was not fully soluble in C7D8 even in the presence of 15-crown-5. After 18 h, NMR spectroscopy showed complete conversion to Cp′3U(BH4). The sample was brought back into the glovebox and the volatiles were removed under reduced pressure. The product was then extracted into Et2O, filtered away from white insoluble solids [presumably Na(15-crown-5)I and excess NaBH4] and the volatiles were removed under reduced pressure to give Cp′3U(BH4) (30 mg, 96%) as a wine-red solid. 1H NMR (C7D8, 500.2 MHz): δ 9.7 (s, C5H4SiMe3, 6H), −2.1 (s, C5H4SiMe3, 27H), −23.1 (s, C5H4SiMe3, 6H), −59.8 (s, br, ν1/2 = 325 Hz, U—(BH4), 4H); 11B{1H} NMR (C7D8, 160.1 MHz): δ 79.1 [s, br, ν1/2 = 230 Hz, U—(BH4)]; 13C{1H} NMR (C7D8, 125.8 MHz): δ 233.1 (C5H4SiMe3), 214.0 (C5H4SiMe3), 185.6 (C5H4SiMe3), 0.4 (C5H4SiMe3); 29Si{1H} NMR (C7D8, 99.1 MHz, INEPT): δ −57.7 (s, C5H4SiMe3); 1H NMR (C6D6, 600.1 MHz): δ 9.6 (s, C5H4SiMe3, 6H), −2.0 (s, C5H4SiMe3, 27H), −22.6 (s, C5H4SiMe3, 6H), −59.3 (s, br, ν1/2 = 300 Hz, U—(BH4), 4H); 11B{1H} NMR (C6D6, 192.6 MHz): δ 79.6 [s, br, ν1/2 = 240 Hz, U-(BH4)]; 13C{1H} NMR (C6D6, 150.9 MHz): δ 232.0 (C5H4SiMe3), 214.2 (C5H4SiMe3), 186.5 (C5H4SiMe3), 0.6 (C5H4SiMe3); 29Si{1H} NMR (C6D6, 119.2 MHz, INEPT): δ −57.4 (s, C5H4SiMe3).
6.3. Cp′3U(BH4) from U(BH4)4 and KCp′
An Et2O (5 mL) solution of KCp′ (460 mg, 2.61 mmol) was added to a pale-green solution of U(BH4)4 (250 mg, 0.841 mmol), also dissolved in Et2O (5 mL). White solids precipitated (presumably KBH4) as the solution quickly turned orange and then slowly changed to dark red (30 min). After stirring the mixture for an additional 12 h, volatiles were removed under reduced pressure, and the product was extracted into hexane leaving white solids behind (presumably KBH4). Removal of the volatiles under reduced pressure gave Cp′3U(BH4) (496 mg, 89%) as a dark wine-red solid. X-ray quality crystals were grown from a concentrated ether solution at 253 K.
7. Refinement
Crystal data, data collection and structure . Analytical scattering factors neutral atoms were used throughout the analysis. A 3-D rendering of the molecule can be found at the following web address: https://submission.iucr.org/jtkt/serve/z/Utgd9EjfTrqJVoXA/zz0000/0/.
details are summarized in Table 2
|
C—H bond distances were constrained to 0.95 Å for cyclopentadienyl C—H moieties, and to 0.98 Å for aliphatic CH3 moieties, respectively. Methyl torsion angles were not refined but constrained to be staggered. The borohydride H atoms were located from a difference-Fourier map and their positions were freely refined. Uiso(H) values were set to a multiple of Ueq(C/B) with 1.5 for CH3 and BH4 and 1.2 for C—H units, respectively.
Supporting information
CCDC reference: 2067867
https://doi.org/10.1107/S2056989021002425/zl5005sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021002425/zl5005Isup3.hkl
Data collection: APEX3 (Bruker, 2018); cell
APEX3 (Bruker, 2018); data reduction: SAINT (Bruker, 2018); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015); molecular graphics: SHELXTL2018/3 (Sheldrick, 2008); software used to prepare material for publication: SHELXTL2018/3 (Sheldrick, 2008).[U(BH4)(C8H13Si)3] | Z = 2 |
Mr = 664.69 | F(000) = 652 |
Triclinic, P1 | Dx = 1.569 Mg m−3 |
a = 8.7530 (15) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.217 (2) Å | Cell parameters from 30231 reflections |
c = 13.657 (2) Å | θ = 2.4–33.1° |
α = 94.159 (3)° | µ = 5.91 mm−1 |
β = 96.016 (3)° | T = 112 K |
γ = 103.256 (3)° | Plate, red |
V = 1406.6 (4) Å3 | 0.88 × 0.62 × 0.17 mm |
Bruker D8 Quest with Photon II detector diffractometer | 9355 reflections with I > 2σ(I) |
Radiation source: IµS 3.0 microfocus | Rint = 0.055 |
ω scans | θmax = 33.1°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −13→13 |
Tmin = 0.413, Tmax = 0.747 | k = −18→18 |
30231 measured reflections | l = −20→20 |
10686 independent 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)] = 0.037 | Hydrogen site location: mixed |
wR(F2) = 0.102 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0549P)2] where P = (Fo2 + 2Fc2)/3 |
10686 reflections | (Δ/σ)max = 0.002 |
274 parameters | Δρmax = 3.87 e Å−3 |
0 restraints | Δρmin = −2.72 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
U1 | 0.51249 (2) | 0.16808 (2) | 0.26353 (2) | 0.00963 (4) | |
B1 | 0.8150 (5) | 0.2329 (4) | 0.3009 (4) | 0.0177 (8) | |
H1A | 0.761 (6) | 0.294 (5) | 0.308 (4) | 0.027* | |
H1B | 0.771 (6) | 0.205 (5) | 0.219 (4) | 0.027* | |
H1C | 0.762 (6) | 0.166 (5) | 0.348 (4) | 0.027* | |
H1D | 0.944 (6) | 0.271 (5) | 0.317 (4) | 0.027* | |
Si1 | 0.76504 (13) | 0.39347 (9) | 0.07862 (8) | 0.0156 (2) | |
Si2 | 0.71528 (13) | 0.35432 (9) | 0.54090 (9) | 0.0161 (2) | |
Si3 | 0.79753 (13) | −0.07373 (10) | 0.23562 (8) | 0.0161 (2) | |
C1 | 0.5747 (4) | 0.3269 (3) | 0.1255 (3) | 0.0134 (6) | |
C2 | 0.4548 (4) | 0.2353 (3) | 0.0762 (3) | 0.0142 (7) | |
H2 | 0.467664 | 0.185642 | 0.022485 | 0.017* | |
C3 | 0.3126 (4) | 0.2291 (3) | 0.1192 (3) | 0.0168 (7) | |
H3A | 0.205686 | 0.182752 | 0.090235 | 0.020* | |
C4 | 0.3423 (5) | 0.3169 (3) | 0.1952 (3) | 0.0194 (8) | |
H4A | 0.259820 | 0.343109 | 0.229549 | 0.023* | |
C5 | 0.5036 (5) | 0.3754 (3) | 0.2021 (3) | 0.0170 (7) | |
H5A | 0.551554 | 0.449334 | 0.242324 | 0.020* | |
C6 | 0.8516 (6) | 0.2832 (4) | 0.0182 (4) | 0.0258 (9) | |
H6A | 0.773894 | 0.237713 | −0.034755 | 0.039* | |
H6B | 0.946750 | 0.320007 | −0.009698 | 0.039* | |
H6C | 0.879493 | 0.234315 | 0.067481 | 0.039* | |
C7 | 0.9080 (5) | 0.4833 (4) | 0.1805 (4) | 0.0259 (9) | |
H7A | 0.935861 | 0.435704 | 0.231009 | 0.039* | |
H7B | 1.003659 | 0.521095 | 0.153741 | 0.039* | |
H7C | 0.859331 | 0.540147 | 0.210342 | 0.039* | |
C8 | 0.7126 (6) | 0.4851 (4) | −0.0173 (4) | 0.0284 (10) | |
H8A | 0.637627 | 0.438442 | −0.070950 | 0.043* | |
H8B | 0.664218 | 0.541988 | 0.012768 | 0.043* | |
H8C | 0.808545 | 0.522937 | −0.043833 | 0.043* | |
C9 | 0.5445 (4) | 0.2558 (3) | 0.4617 (3) | 0.0139 (6) | |
C10 | 0.5031 (4) | 0.1358 (3) | 0.4589 (3) | 0.0129 (6) | |
H10A | 0.566960 | 0.090586 | 0.496241 | 0.016* | |
C11 | 0.3457 (4) | 0.0938 (3) | 0.4159 (3) | 0.0148 (7) | |
H11A | 0.280490 | 0.015468 | 0.418243 | 0.018* | |
C12 | 0.2877 (4) | 0.1864 (3) | 0.3859 (3) | 0.0159 (7) | |
H12A | 0.174487 | 0.184244 | 0.363546 | 0.019* | |
C13 | 0.4089 (5) | 0.2856 (3) | 0.4155 (3) | 0.0156 (7) | |
H13 | 0.400650 | 0.360371 | 0.406008 | 0.019* | |
C14 | 0.7834 (5) | 0.4881 (3) | 0.4818 (4) | 0.0236 (9) | |
H14A | 0.694252 | 0.523095 | 0.467930 | 0.035* | |
H14B | 0.867433 | 0.540488 | 0.526781 | 0.035* | |
H14C | 0.823995 | 0.470669 | 0.419794 | 0.035* | |
C15 | 0.6386 (6) | 0.3890 (4) | 0.6594 (3) | 0.0269 (9) | |
H15A | 0.553651 | 0.428013 | 0.645944 | 0.040* | |
H15B | 0.597529 | 0.319142 | 0.688904 | 0.040* | |
H15C | 0.724665 | 0.438154 | 0.705407 | 0.040* | |
C16 | 0.8764 (5) | 0.2804 (4) | 0.5706 (3) | 0.0226 (8) | |
H16A | 0.965381 | 0.332556 | 0.612059 | 0.034* | |
H16B | 0.836522 | 0.215057 | 0.606193 | 0.034* | |
H16C | 0.911947 | 0.254911 | 0.509097 | 0.034* | |
C17 | 0.6012 (4) | −0.0360 (3) | 0.2171 (3) | 0.0128 (6) | |
C18 | 0.4764 (5) | −0.0648 (3) | 0.2755 (3) | 0.0140 (6) | |
H18 | 0.485999 | −0.088223 | 0.340226 | 0.017* | |
C19 | 0.3343 (4) | −0.0530 (3) | 0.2215 (3) | 0.0153 (7) | |
H19 | 0.232617 | −0.068713 | 0.243279 | 0.018* | |
C20 | 0.3699 (4) | −0.0141 (3) | 0.1306 (3) | 0.0145 (7) | |
H20A | 0.290811 | −0.013775 | 0.072251 | 0.017* | |
C21 | 0.5350 (4) | −0.0017 (3) | 0.1283 (3) | 0.0130 (6) | |
H21A | 0.589324 | 0.009939 | 0.067662 | 0.016* | |
C22 | 0.8854 (5) | −0.0487 (4) | 0.3683 (3) | 0.0238 (9) | |
H22A | 0.904791 | 0.031903 | 0.390761 | 0.036* | |
H22B | 0.811913 | −0.092648 | 0.408388 | 0.036* | |
H22C | 0.985486 | −0.072076 | 0.375288 | 0.036* | |
C23 | 0.7622 (7) | −0.2283 (4) | 0.1955 (4) | 0.0334 (11) | |
H23A | 0.716059 | −0.243268 | 0.125928 | 0.050* | |
H23B | 0.862889 | −0.250933 | 0.203265 | 0.050* | |
H23C | 0.689316 | −0.271505 | 0.236365 | 0.050* | |
C24 | 0.9339 (5) | 0.0070 (4) | 0.1537 (4) | 0.0277 (10) | |
H24A | 0.883975 | −0.008159 | 0.084891 | 0.042* | |
H24B | 0.954902 | 0.088142 | 0.174393 | 0.042* | |
H24C | 1.033665 | −0.016878 | 0.159288 | 0.042* |
U11 | U22 | U33 | U12 | U13 | U23 | |
U1 | 0.00980 (6) | 0.01025 (6) | 0.00983 (7) | 0.00336 (4) | 0.00194 (4) | 0.00341 (4) |
B1 | 0.0131 (18) | 0.019 (2) | 0.021 (2) | 0.0041 (15) | 0.0016 (16) | 0.0059 (16) |
Si1 | 0.0167 (5) | 0.0131 (4) | 0.0176 (5) | 0.0025 (4) | 0.0052 (4) | 0.0052 (4) |
Si2 | 0.0188 (5) | 0.0123 (4) | 0.0163 (5) | 0.0030 (4) | 0.0004 (4) | 0.0002 (4) |
Si3 | 0.0160 (5) | 0.0195 (5) | 0.0161 (5) | 0.0099 (4) | 0.0025 (4) | 0.0049 (4) |
C1 | 0.0143 (15) | 0.0126 (15) | 0.0135 (16) | 0.0032 (12) | 0.0010 (12) | 0.0050 (12) |
C2 | 0.0163 (16) | 0.0158 (16) | 0.0109 (16) | 0.0038 (13) | 0.0015 (13) | 0.0037 (12) |
C3 | 0.0140 (16) | 0.0207 (18) | 0.0172 (18) | 0.0051 (13) | 0.0010 (13) | 0.0098 (14) |
C4 | 0.0163 (17) | 0.0192 (18) | 0.028 (2) | 0.0106 (14) | 0.0061 (15) | 0.0141 (16) |
C5 | 0.0186 (17) | 0.0148 (16) | 0.0210 (19) | 0.0079 (13) | 0.0051 (14) | 0.0091 (14) |
C6 | 0.030 (2) | 0.020 (2) | 0.029 (2) | 0.0048 (17) | 0.0154 (19) | 0.0026 (17) |
C7 | 0.024 (2) | 0.021 (2) | 0.030 (2) | −0.0006 (16) | 0.0056 (18) | 0.0030 (17) |
C8 | 0.028 (2) | 0.029 (2) | 0.032 (3) | 0.0063 (18) | 0.0100 (19) | 0.021 (2) |
C9 | 0.0145 (15) | 0.0117 (15) | 0.0165 (17) | 0.0045 (12) | 0.0024 (13) | 0.0022 (12) |
C10 | 0.0168 (16) | 0.0122 (15) | 0.0102 (15) | 0.0033 (12) | 0.0028 (12) | 0.0028 (12) |
C11 | 0.0148 (15) | 0.0169 (16) | 0.0132 (16) | 0.0016 (13) | 0.0061 (13) | 0.0057 (13) |
C12 | 0.0119 (15) | 0.0236 (18) | 0.0143 (17) | 0.0067 (13) | 0.0046 (13) | 0.0026 (14) |
C13 | 0.0167 (16) | 0.0175 (17) | 0.0145 (17) | 0.0076 (13) | 0.0025 (13) | 0.0023 (13) |
C14 | 0.026 (2) | 0.0122 (17) | 0.032 (2) | 0.0031 (15) | 0.0054 (18) | 0.0032 (16) |
C15 | 0.037 (2) | 0.023 (2) | 0.018 (2) | 0.0031 (18) | 0.0037 (18) | −0.0048 (16) |
C16 | 0.0228 (19) | 0.0204 (19) | 0.025 (2) | 0.0080 (15) | −0.0036 (16) | 0.0027 (16) |
C17 | 0.0141 (15) | 0.0125 (15) | 0.0126 (16) | 0.0041 (12) | 0.0025 (12) | 0.0029 (12) |
C18 | 0.0190 (17) | 0.0126 (15) | 0.0104 (16) | 0.0033 (13) | 0.0025 (13) | 0.0024 (12) |
C19 | 0.0137 (15) | 0.0127 (15) | 0.0182 (18) | −0.0003 (12) | 0.0032 (13) | 0.0031 (13) |
C20 | 0.0140 (15) | 0.0176 (16) | 0.0097 (16) | 0.0018 (13) | −0.0030 (12) | −0.0001 (12) |
C21 | 0.0149 (16) | 0.0140 (15) | 0.0111 (16) | 0.0063 (12) | 0.0007 (12) | −0.0007 (12) |
C22 | 0.0220 (19) | 0.033 (2) | 0.020 (2) | 0.0142 (17) | 0.0007 (16) | 0.0059 (17) |
C23 | 0.040 (3) | 0.025 (2) | 0.041 (3) | 0.022 (2) | 0.001 (2) | −0.001 (2) |
C24 | 0.023 (2) | 0.038 (3) | 0.030 (2) | 0.0164 (19) | 0.0102 (18) | 0.014 (2) |
U1—B1 | 2.568 (4) | C7—H7B | 0.9800 |
U1—C21 | 2.731 (4) | C7—H7C | 0.9800 |
U1—C10 | 2.732 (4) | C8—H8A | 0.9800 |
U1—C20 | 2.733 (4) | C8—H8B | 0.9800 |
U1—C5 | 2.740 (4) | C8—H8C | 0.9800 |
U1—C12 | 2.748 (4) | C9—C13 | 1.419 (5) |
U1—C11 | 2.754 (3) | C9—C10 | 1.424 (5) |
U1—C4 | 2.755 (4) | C10—C11 | 1.403 (5) |
U1—C3 | 2.755 (4) | C10—H10A | 1.0000 |
U1—H1A | 2.35 (5) | C11—C12 | 1.411 (5) |
U1—H1B | 2.35 (5) | C11—H11A | 1.0000 |
U1—H1C | 2.36 (5) | C12—C13 | 1.417 (5) |
B1—H1A | 0.98 (6) | C12—H12A | 1.0000 |
B1—H1B | 1.15 (6) | C13—H13 | 0.9500 |
B1—H1C | 1.12 (5) | C14—H14A | 0.9800 |
B1—H1D | 1.11 (5) | C14—H14B | 0.9800 |
Si1—C7 | 1.868 (5) | C14—H14C | 0.9800 |
Si1—C8 | 1.871 (4) | C15—H15A | 0.9800 |
Si1—C6 | 1.872 (5) | C15—H15B | 0.9800 |
Si1—C1 | 1.877 (4) | C15—H15C | 0.9800 |
Si2—C16 | 1.867 (4) | C16—H16A | 0.9800 |
Si2—C9 | 1.871 (4) | C16—H16B | 0.9800 |
Si2—C15 | 1.873 (5) | C16—H16C | 0.9800 |
Si2—C14 | 1.877 (4) | C17—C18 | 1.415 (5) |
Si3—C22 | 1.867 (5) | C17—C21 | 1.421 (5) |
Si3—C23 | 1.873 (5) | C18—C19 | 1.420 (5) |
Si3—C17 | 1.876 (4) | C18—H18 | 0.9500 |
Si3—C24 | 1.884 (5) | C19—C20 | 1.402 (5) |
C1—C2 | 1.418 (5) | C19—H19 | 0.9500 |
C1—C5 | 1.432 (6) | C20—C21 | 1.421 (5) |
C2—C3 | 1.420 (5) | C20—H20A | 1.0000 |
C2—H2 | 0.9500 | C21—H21A | 1.0000 |
C3—C4 | 1.396 (6) | C22—H22A | 0.9800 |
C3—H3A | 1.0000 | C22—H22B | 0.9800 |
C4—C5 | 1.418 (5) | C22—H22C | 0.9800 |
C4—H4A | 1.0000 | C23—H23A | 0.9800 |
C5—H5A | 1.0000 | C23—H23B | 0.9800 |
C6—H6A | 0.9800 | C23—H23C | 0.9800 |
C6—H6B | 0.9800 | C24—H24A | 0.9800 |
C6—H6C | 0.9800 | C24—H24B | 0.9800 |
C7—H7A | 0.9800 | C24—H24C | 0.9800 |
B1—U1—C21 | 91.29 (14) | C3—C4—H4A | 125.3 |
B1—U1—C10 | 88.27 (13) | C5—C4—H4A | 125.3 |
C21—U1—C10 | 121.25 (11) | U1—C4—H4A | 125.3 |
B1—U1—C20 | 121.42 (14) | C4—C5—C1 | 108.8 (4) |
C21—U1—C20 | 30.15 (11) | C4—C5—U1 | 75.7 (2) |
C10—U1—C20 | 116.28 (11) | C1—C5—U1 | 77.6 (2) |
B1—U1—C5 | 89.68 (13) | C4—C5—H5A | 124.8 |
C21—U1—C5 | 119.23 (12) | C1—C5—H5A | 124.8 |
C10—U1—C5 | 119.52 (12) | U1—C5—H5A | 124.8 |
C20—U1—C5 | 115.78 (12) | Si1—C6—H6A | 109.5 |
B1—U1—C12 | 128.78 (14) | Si1—C6—H6B | 109.5 |
C21—U1—C12 | 131.96 (12) | H6A—C6—H6B | 109.5 |
C10—U1—C12 | 48.97 (11) | Si1—C6—H6C | 109.5 |
C20—U1—C12 | 104.45 (12) | H6A—C6—H6C | 109.5 |
C5—U1—C12 | 89.90 (12) | H6B—C6—H6C | 109.5 |
B1—U1—C11 | 117.73 (13) | Si1—C7—H7A | 109.5 |
C21—U1—C11 | 113.80 (11) | Si1—C7—H7B | 109.5 |
C10—U1—C11 | 29.63 (11) | H7A—C7—H7B | 109.5 |
C20—U1—C11 | 95.57 (11) | Si1—C7—H7C | 109.5 |
C5—U1—C11 | 118.89 (12) | H7A—C7—H7C | 109.5 |
C12—U1—C11 | 29.73 (11) | H7B—C7—H7C | 109.5 |
B1—U1—C4 | 119.54 (13) | Si1—C8—H8A | 109.5 |
C21—U1—C4 | 115.96 (13) | Si1—C8—H8B | 109.5 |
C10—U1—C4 | 114.79 (12) | H8A—C8—H8B | 109.5 |
C20—U1—C4 | 98.00 (13) | Si1—C8—H8C | 109.5 |
C5—U1—C4 | 29.91 (11) | H8A—C8—H8C | 109.5 |
C12—U1—C4 | 70.43 (12) | H8B—C8—H8C | 109.5 |
C11—U1—C4 | 99.66 (12) | C13—C9—C10 | 105.6 (3) |
B1—U1—C3 | 129.05 (13) | C13—C9—Si2 | 125.9 (3) |
C21—U1—C3 | 87.02 (12) | C10—C9—Si2 | 126.4 (3) |
C10—U1—C3 | 134.56 (12) | C11—C10—C9 | 109.8 (3) |
C20—U1—C3 | 69.70 (12) | C11—C10—U1 | 76.0 (2) |
C5—U1—C3 | 49.08 (12) | C9—C10—U1 | 77.7 (2) |
C12—U1—C3 | 85.59 (12) | C11—C10—H10A | 124.4 |
C11—U1—C3 | 109.24 (11) | C9—C10—H10A | 124.4 |
C4—U1—C3 | 29.34 (13) | U1—C10—H10A | 124.4 |
B1—U1—H1A | 22.4 (14) | C10—C11—C12 | 107.6 (3) |
C21—U1—H1A | 110.3 (14) | C10—C11—U1 | 74.3 (2) |
C10—U1—H1A | 88.4 (14) | C12—C11—U1 | 74.9 (2) |
C20—U1—H1A | 139.8 (14) | C10—C11—H11A | 125.7 |
C5—U1—H1A | 70.3 (13) | C12—C11—H11A | 125.7 |
C12—U1—H1A | 115.5 (14) | U1—C11—H11A | 125.7 |
C11—U1—H1A | 116.7 (14) | C11—C12—C13 | 107.6 (3) |
C4—U1—H1A | 99.3 (13) | C11—C12—U1 | 75.4 (2) |
C3—U1—H1A | 116.2 (13) | C13—C12—U1 | 76.6 (2) |
B1—U1—H1B | 26.5 (14) | C11—C12—H12A | 125.4 |
C21—U1—H1B | 70.8 (14) | C13—C12—H12A | 125.4 |
C10—U1—H1B | 113.0 (14) | U1—C12—H12A | 125.4 |
C20—U1—H1B | 100.0 (14) | C12—C13—C9 | 109.4 (3) |
C5—U1—H1B | 85.6 (13) | C12—C13—H13 | 125.3 |
C12—U1—H1B | 154.6 (14) | C9—C13—H13 | 125.3 |
C11—U1—H1B | 141.1 (13) | Si2—C14—H14A | 109.5 |
C4—U1—H1B | 113.1 (13) | Si2—C14—H14B | 109.5 |
C3—U1—H1B | 109.6 (13) | H14A—C14—H14B | 109.5 |
H1A—U1—H1B | 39.9 (19) | Si2—C14—H14C | 109.5 |
B1—U1—H1C | 25.8 (13) | H14A—C14—H14C | 109.5 |
C21—U1—H1C | 90.4 (14) | H14B—C14—H14C | 109.5 |
C10—U1—H1C | 66.9 (14) | Si2—C15—H15A | 109.5 |
C20—U1—H1C | 116.7 (13) | Si2—C15—H15B | 109.5 |
C5—U1—H1C | 112.4 (13) | H15A—C15—H15B | 109.5 |
C12—U1—H1C | 114.2 (14) | Si2—C15—H15C | 109.5 |
C11—U1—H1C | 94.8 (13) | H15A—C15—H15C | 109.5 |
C4—U1—H1C | 140.7 (13) | H15B—C15—H15C | 109.5 |
C3—U1—H1C | 154.7 (13) | Si2—C16—H16A | 109.5 |
H1A—U1—H1C | 42.1 (18) | Si2—C16—H16B | 109.5 |
H1B—U1—H1C | 46.4 (18) | H16A—C16—H16B | 109.5 |
U1—B1—H1A | 66 (3) | Si2—C16—H16C | 109.5 |
U1—B1—H1B | 66 (3) | H16A—C16—H16C | 109.5 |
H1A—B1—H1B | 97 (4) | H16B—C16—H16C | 109.5 |
U1—B1—H1C | 67 (3) | C18—C17—C21 | 106.5 (3) |
H1A—B1—H1C | 107 (4) | C18—C17—Si3 | 126.3 (3) |
H1B—B1—H1C | 110 (4) | C21—C17—Si3 | 125.2 (3) |
U1—B1—H1D | 174 (3) | C17—C18—C19 | 108.8 (3) |
H1A—B1—H1D | 108 (4) | C17—C18—H18 | 125.6 |
H1B—B1—H1D | 115 (4) | C19—C18—H18 | 125.6 |
H1C—B1—H1D | 118 (4) | C20—C19—C18 | 108.2 (3) |
C7—Si1—C8 | 109.1 (2) | C20—C19—H19 | 125.9 |
C7—Si1—C6 | 111.5 (2) | C18—C19—H19 | 125.9 |
C8—Si1—C6 | 108.4 (2) | C19—C20—C21 | 107.5 (3) |
C7—Si1—C1 | 110.74 (19) | C19—C20—U1 | 77.0 (2) |
C8—Si1—C1 | 106.02 (19) | C21—C20—U1 | 74.8 (2) |
C6—Si1—C1 | 110.83 (18) | C19—C20—H20A | 125.5 |
C16—Si2—C9 | 109.96 (19) | C21—C20—H20A | 125.5 |
C16—Si2—C15 | 107.7 (2) | U1—C20—H20A | 125.5 |
C9—Si2—C15 | 105.7 (2) | C20—C21—C17 | 109.0 (3) |
C16—Si2—C14 | 113.1 (2) | C20—C21—U1 | 75.0 (2) |
C9—Si2—C14 | 111.05 (19) | C17—C21—U1 | 78.9 (2) |
C15—Si2—C14 | 109.0 (2) | C20—C21—H21A | 124.6 |
C22—Si3—C23 | 108.2 (2) | C17—C21—H21A | 124.6 |
C22—Si3—C17 | 111.93 (19) | U1—C21—H21A | 124.6 |
C23—Si3—C17 | 107.1 (2) | Si3—C22—H22A | 109.5 |
C22—Si3—C24 | 111.8 (2) | Si3—C22—H22B | 109.5 |
C23—Si3—C24 | 108.4 (3) | H22A—C22—H22B | 109.5 |
C17—Si3—C24 | 109.23 (18) | Si3—C22—H22C | 109.5 |
C2—C1—C5 | 105.6 (3) | H22A—C22—H22C | 109.5 |
C2—C1—Si1 | 126.1 (3) | H22B—C22—H22C | 109.5 |
C5—C1—Si1 | 126.4 (3) | Si3—C23—H23A | 109.5 |
C1—C2—C3 | 109.7 (4) | Si3—C23—H23B | 109.5 |
C1—C2—H2 | 125.2 | H23A—C23—H23B | 109.5 |
C3—C2—H2 | 125.2 | Si3—C23—H23C | 109.5 |
C4—C3—C2 | 107.5 (3) | H23A—C23—H23C | 109.5 |
C4—C3—U1 | 75.3 (2) | H23B—C23—H23C | 109.5 |
C2—C3—U1 | 75.9 (2) | Si3—C24—H24A | 109.5 |
C4—C3—H3A | 125.5 | Si3—C24—H24B | 109.5 |
C2—C3—H3A | 125.5 | H24A—C24—H24B | 109.5 |
U1—C3—H3A | 125.5 | Si3—C24—H24C | 109.5 |
C3—C4—C5 | 108.4 (4) | H24A—C24—H24C | 109.5 |
C3—C4—U1 | 75.3 (2) | H24B—C24—H24C | 109.5 |
C5—C4—U1 | 74.4 (2) | ||
C7—Si1—C1—C2 | −164.8 (3) | Si2—C9—C10—U1 | −128.1 (3) |
C8—Si1—C1—C2 | 76.9 (4) | C9—C10—C11—C12 | 3.1 (4) |
C6—Si1—C1—C2 | −40.5 (4) | U1—C10—C11—C12 | −68.1 (3) |
C7—Si1—C1—C5 | 33.1 (4) | C9—C10—C11—U1 | 71.2 (3) |
C8—Si1—C1—C5 | −85.2 (4) | C10—C11—C12—C13 | −2.8 (4) |
C6—Si1—C1—C5 | 157.4 (3) | U1—C11—C12—C13 | −70.5 (3) |
C5—C1—C2—C3 | 1.5 (4) | C10—C11—C12—U1 | 67.7 (3) |
Si1—C1—C2—C3 | −163.6 (3) | C11—C12—C13—C9 | 1.6 (4) |
C1—C2—C3—C4 | 0.3 (4) | U1—C12—C13—C9 | −68.1 (3) |
C1—C2—C3—U1 | −69.1 (3) | C10—C9—C13—C12 | 0.3 (4) |
C2—C3—C4—C5 | −2.0 (4) | Si2—C9—C13—C12 | −163.7 (3) |
U1—C3—C4—C5 | 67.7 (3) | C22—Si3—C17—C18 | −45.2 (4) |
C2—C3—C4—U1 | −69.7 (3) | C23—Si3—C17—C18 | 73.3 (4) |
C3—C4—C5—C1 | 3.0 (4) | C24—Si3—C17—C18 | −169.5 (4) |
U1—C4—C5—C1 | 71.3 (3) | C22—Si3—C17—C21 | 153.2 (3) |
C3—C4—C5—U1 | −68.3 (3) | C23—Si3—C17—C21 | −88.3 (4) |
C2—C1—C5—C4 | −2.8 (4) | C24—Si3—C17—C21 | 28.9 (4) |
Si1—C1—C5—C4 | 162.3 (3) | C21—C17—C18—C19 | 2.5 (4) |
C2—C1—C5—U1 | 67.2 (2) | Si3—C17—C18—C19 | −161.9 (3) |
Si1—C1—C5—U1 | −127.7 (3) | C17—C18—C19—C20 | −1.5 (4) |
C16—Si2—C9—C13 | −172.4 (3) | C18—C19—C20—C21 | 0.0 (4) |
C15—Si2—C9—C13 | 71.6 (4) | C18—C19—C20—U1 | −69.3 (3) |
C14—Si2—C9—C13 | −46.5 (4) | C19—C20—C21—C17 | 1.6 (4) |
C16—Si2—C9—C10 | 26.8 (4) | U1—C20—C21—C17 | 72.3 (3) |
C15—Si2—C9—C10 | −89.2 (4) | C19—C20—C21—U1 | −70.8 (3) |
C14—Si2—C9—C10 | 152.7 (3) | C18—C17—C21—C20 | −2.5 (4) |
C13—C9—C10—C11 | −2.1 (4) | Si3—C17—C21—C20 | 162.1 (3) |
Si2—C9—C10—C11 | 161.8 (3) | C18—C17—C21—U1 | 67.2 (3) |
C13—C9—C10—U1 | 68.0 (3) | Si3—C17—C21—U1 | −128.1 (3) |
cent = C5H4SiMe3 centroid. |
Cp'3U(BH4) | Cp'3UCla (Windorff et al., 2017) | Cp'3UI (Windorff et al., 2017) | Cp'3U(η1-CH═CH2) (Schock et al., 1988) | Cp'3U[Si(SiMe3)3] (Réant et al., 2020) | |
U—(cent) | 2.458, 2.490, 2.500 | 2.473 | 2.475, 2.478, 2.480 | 2.481, 2.483, 2.489 | 2.472, 2.478, 2.485 |
(cent)—U—X | 104.13, 104.14, 104.83 | 100.00 | 97.9, 101.2, 101.6 | 95.1 100.0 100.2 | 96.04, 96.30, 97.65 |
(cent)—U—(cent) | 113.28, 114.26, 114.26 | 117.00 | 116.1, 116.4, 118.3 | 116.4, 117.2, 120.0 | 118.28, 118.88, 119.08 |
Note: (a) The asymmetric unit contains one Cp' ring, one-third of a chloride atom, and one-third of a uranium atom. |
Footnotes
‡Present address: New Mexico State University, Department of Chemistry and Biochemistry, Las Cruces, NM 88003, USA.
Acknowledgements
We wish to thank Robert T. Pain (University of New Mexico) for the gift of U(BH4)4. We also wish to thank Dr Joseph W. Ziller (UC-Irvine) for helpful discussions.
Funding information
Funding for this research was provided by: U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Heavy Element Chemistry program (grant No. 2020LANLE372 to SAK, BLS; grant No. DE-SC0004739 to WJE); U.S. Department of Energy, Office of Science, Office of Workforce Development for Teachers and Scientists, Oak Ridge Institute for Science and Education (ORISE), Office of Science Graduate Student Research (SCGSR) program. (contract No. DE-AC05-06OR23100 to CJW); Los Alamos, Director's Postdoctoral Fellowship (award to JNC); U.S. Department of Energy, NNSA, Triad National Security, LLC (contract No. 89233218CNA000001).
References
Arliguie, T., Blug, M., Le Floch, P., Mézailles, N., Thuéry, P. & Ephritikhine, M. (2008). Organometallics, 27, 4158–4165. Web of Science CSD CrossRef CAS Google Scholar
Arnold, P. L., Farnaby, J. H., Gardiner, M. G. & Love, J. B. (2015). Organometallics, 34, 2114–2117. Web of Science CSD CrossRef CAS Google Scholar
Baudry, D., Bulot, E., Charpin, P., Ephritikhine, M., Lance, M., Nierlich, M. & Vigner, J. (1989). J. Organomet. Chem. 371, 163–174. CSD CrossRef CAS Web of Science Google Scholar
Baudry, D., Charpin, P., Ephritikhine, M., Folcher, G., Lambard, J., Lance, M., Nierlich, M. & Vigner, J. (1985). J. Chem. Soc. Chem. Commun. pp. 1553–1554. CrossRef Web of Science Google Scholar
Baudry, D., Ephritikhine, M., Nief, F., Ricard, L. & Mathey, F. (1990). Angew. Chem. Int. Ed. Engl. 29, 1485–1486. CSD CrossRef Web of Science Google Scholar
Bernstein, E. R., Hamilton, W. C., Keiderling, T. A., La Placa, S. J., Lippard, S. J. & Mayerle, J. J. (1972). Inorg. Chem. 11, 3009–3016. CSD CrossRef CAS Web of Science Google Scholar
Berthet, J.-C. & Ephritikhine, M. (1992). New J. Chem. 16, 767–768. CAS Google Scholar
Berthet, J.-C., Le Maréchal, J.-F., Nierlich, M., Lance, M., Vigner, J. & Ephritikhine, M. (1991). J. Organomet. Chem. 408, 335–341. CSD CrossRef CAS Web of Science Google Scholar
Blake, P. C., Lappert, M. F., Taylor, R. G., Atwood, J. L., Hunter, W. E. & Zhang, H. (1995). J. Chem. Soc. Dalton Trans. pp. 3335–3341. CrossRef Web of Science Google Scholar
Bruker (2018). APEX3, and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cendrowski-Guillaume, S. M., Nierlich, M. & Ephritikhine, M. (2002). J. Organomet. Chem. 643–644, 209–213. CAS Google Scholar
Daly, S. R., Ephritikhine, M. & Girolami, G. S. (2012). Polyhedron, 33, 41–44. Web of Science CSD CrossRef CAS Google Scholar
Daly, S. R. & Girolami, G. S. (2010). Chem. Commun. 46, 407–408. Web of Science CSD CrossRef ICSD CAS Google Scholar
Daly, S. R., Piccoli, P. M., Schultz, A. J., Todorova, T. K., Gagliardi, L. & Girolami, G. S. (2010). Angew. Chem. Int. Ed. 49, 3379–3381. Web of Science CSD CrossRef CAS Google Scholar
Elkechai, A., Boucekkine, A., Belkhiri, L., Amarouche, M., Clappe, C., Hauchard, D. & Ephritikhine, M. (2009). Dalton Trans. pp. 2843–2849. Web of Science CrossRef Google Scholar
Ephritikhine, M. (1997). Chem. Rev. 97, 2193–2242. CrossRef PubMed CAS Web of Science Google Scholar
Gradoz, P., Baudry, D., Ephritikhine, M., Lance, M., Nierlich, M. & Vigner, J. (1994). J. Organomet. Chem. 466, 107–118. CSD CrossRef CAS Web of Science Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Hoekstra, H. R. & Katz, J. J. (1949). J. Am. Chem. Soc. 71, 2488–2492. CrossRef CAS Web of Science Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef ICSD CAS IUCr Journals Google Scholar
Liptrot, D. J., Guo, J.-D., Nagase, S. & Power, P. P. (2016). Angew. Chem. Int. Ed. 55, 14766–14769. Web of Science CrossRef CAS Google Scholar
MacDonald, M. R., Fieser, M. E., Bates, J. E., Ziller, J. W., Furche, F. & Evans, W. J. (2013). J. Am. Chem. Soc. 135, 13310–13313. Web of Science CSD CrossRef CAS PubMed Google Scholar
Marsh, R. E., Kapon, M., Hu, S. & Herbstein, F. H. (2002). Acta Cryst. B58, 62–77. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Mehdoui, T., Berthet, J.-C., Thuéry, P. & Ephritikhine, M. (2004). Eur. J. Inorg. Chem. pp. 1996–2000. Web of Science CSD CrossRef Google Scholar
Peterson, J. K., MacDonald, M. R., Ziller, J. W. & Evans, W. J. (2013). Organometallics, 32, 2625–2631. Web of Science CSD CrossRef CAS Google Scholar
Réant, B. L. L., Berryman, V. E. J., Seed, J. A., Basford, A. R., Formanuik, A., Wooles, A. J., Kaltsoyannis, N., Liddle, S. T. & Mills, D. P. (2020). Chem. Commun. 56, 12620–12623. Google Scholar
Rebizant, J., Spirlet, M. R., Bettonville, S. & Goffart, J. (1989). Acta Cryst. C45, 1509–1511. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Ryan, R. R., Salazar, K. V., Sauer, N. N. & Ritchey, J. M. (1989). Inorg. Chim. Acta, 162, 221–225. CSD CrossRef CAS Web of Science Google Scholar
Schlesinger, H. I. & Brown, H. C. (1953). J. Am. Chem. Soc. 75, 219–221. CrossRef CAS Web of Science Google Scholar
Schock, L. E., Seyam, A. M., Sabat, M. & Marks, T. J. (1988). Polyhedron, 7, 1517–1529. CSD CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Tsoureas, N. & Cloke, F. G. N. (2018). Chem. Commun. 54, 8830–8833. Web of Science CSD CrossRef CAS Google Scholar
Wedal, J. C., Bekoe, S., Ziller, J. W., Furche, F. & Evans, W. J. (2019). Dalton Trans. 48, 16633–16640. Web of Science CSD CrossRef CAS PubMed Google Scholar
Windorff, C. J. & Evans, W. J. (2014). Organometallics, 33, 3786–3791. Web of Science CrossRef CAS Google Scholar
Windorff, C. J., MacDonald, M. R., Ziller, J. W. & Evans, W. J. (2017). Z. Anorg. Allg. Chem. 643, 2011–2018. Web of Science CSD CrossRef CAS Google Scholar
Zanella, P., Brianese, N., Casellato, U., Ossola, F., Porchia, M., Rossetto, G. & Graziani, R. (1988). Inorg. Chim. Acta, 144, 129–134. CrossRef CAS Web of Science Google Scholar
Zanella, P., De Paoli, G., Bombieri, G., Zanotti, G. & Rossi, R. (1977). J. Organomet. Chem. 142, C21–C24. CSD CrossRef CAS Web of Science Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.