Synthesis of Actinide Fluoride Complexes Using Trimethyltin Fluoride as a Mild and Selective Fluorinating Reagent

Article abstract of DOI:10.1002/ejic.201701232

Trimethyltin fluoride (Me₃SnF) is a mild and selective reagent for the installation of actinide fluoride bonds as demonstrated by the room temperature synthesis of a variety of organometallic and inorganic thorium(IV), uranium(IV), and uranium(

Full text of DOI:10.1002/ejic.201701232

DOI: 10.1002/ejic.201701232
Full Paper
Fluorinating Reagents | Very Important Paper |
Synthesis of Actinide Fluoride Complexes Using Trimethyltin
Fluoride as a Mild and Selective Fluorinating Reagent
Benjamin D. Kagan,[a,b] Alejandro G. Lichtscheidl,[a] Karla A. Erickson,[a] Marisa J. Monreal,[a]
Brian L. Scott,[c] Andrew T. Nelson,[d] and Jaqueline L. Kiplinger*[a]
Abstract: Trimethyltin fluoride (Me3SnF) is a mild and selective (C5Me5)2UF2(L) (L
=
O=PMe3, O=PPh3, O=PCy3), and
reagent for the installation of actinide fluoride bonds as dem- (C5Me5)2U(F)(=N-2,6-iPr2C6H3)} from their corresponding chlor-
onstrated by the room temperature synthesis of a variety of ide, bromide, and iodide analogues. From these reactions, the
organometallic and inorganic thorium(IV), uranium(IV), and new (C5Me5)2UF2(L) (L = O=PPh3, O=PCy3) uranium fluoride
uranium(V) fluoride complexes {(1,2,4-tBu3C5H2)2ThF2, (C5Me5)2- complexes were isolated and characterized by NMR spectro-
U(F)(O-2,6-iPr2C6H3), U(F)(O-2,6-tBu2C6H3)3, U(F)[N(SiMe3)2]3, scopy and X-ray crystallography.
Introduction
have vastly improved, enabling a variety of new approaches for
synthesizing molecular organometallic compounds containing
actinide fluoride bonds.
Actinide fluorine chemistry has been studied since the Manhat-
tan project, where volatile separations of uranium isotopes
were sought.[1] As the most volatile uranium compound, UF6
was selected for isotope separations using the gaseous diffu-
sion method; however, using UF6 was complicated by its high
reactivity and due to problems associated with its handling.
Nevertheless, a major consequence of the gaseous diffusion
process has been the accumulation of a significant amount of
depleted UF6.[2] As such, understanding the chemistry of the
U–F bond has important implications for evaluating technolo-
gies for the storage, disposal, or re-use of depleted UF6.
Archetypal methods for synthesizing organometallic ura-
nium fluoride compounds have evolved from redox chemistry
with inorganic [AgBF4,[6] AgF,[7] AgPF6,[8] CuF2,[9] HgF2,[10]
PF3,[7,11] (Ph3P)AuCF3[12]] and organic (C6H5F,[10] Me3SiCF3,[13]
COF2,[7] PhCOF,[14] Ph3CF[7]) fluoride reagents. In the area of
thorium chemistry, thorium bipyridyl metallocene complexes
react with AgF to give thorium fluoride derivatives.[15] The re-
duction of metallocene difluoride complexes has also proved
to be
a practical method for preparing trivalent fluor-
ides.[6a,6b,16] Boron trifluoride (BF3·OEt2) has been used as a
fluoride exchange reagent to yield uranium fluorides upon reac-
tions with metallocene uranium alkoxide,[17] alkyl,[17,18] and
amide[17] complexes. Fluoride atom abstraction from aromatic
and aliphatic fluorocarbons by (MeC5H4)3U(tBu) has also been
shown to give (MeC5H4)3UF in high yields.[7,19] Similarly, the ura-
nium(III) alkyl Tp*2UCH2Ph activates C–F bonds on a variety of
fluorinated substrates to yield Tp*2UF and Tp*2UF2 [Tp* =
hydrotris(3,5-dimethylpyrazolyl)borate].[20] Finally, protonolysis
chemistry between uranium alkyl compounds using
NEt3·3HF[21] and NH4F[22] has been employed to afford uranium
fluoride complexes.
Despite the obvious experimental challenges, there is con-
siderable interest in developing methods for the preparation of
stable inorganic and organometallic actinide fluoride com-
plexes as these molecules may provide crucial information re-
garding the poorly understood chemistry of actinide fluorides.
In fact, there are only a couple of early accounts that report
well-characterized reactivity of UF6 with MeOH and Me3SiOMe
to give (MeO)UF5 and U(OMe)6,[4] respectively. Even in the
[3]
presence of trace water, UF6 reacts to form HF and uranium
oxides, making the study of UF6 and its chemistry challeng-
ing.[5] Over the past decade, this has changed. Techniques for
handling and characterizing air- and water-sensitive materials
Generally speaking, these existing routes to actinide fluoride
complexes are limited and substrate specific. We have been in-
vestigating new methods for the synthesis of thorium and ura-
nium fluoride complexes to explore their chemistry and sought
to use trimethyltin fluoride (Me3SnF) as a fluorinating reagent.
Roesky and co-workers pioneered the use of Me3SnF as a rea-
gent for the metathesis of chlorides to the corresponding fluor-
ides.[23] Although this compound forms a polymeric chain-like
structure of tin and fluorine atoms in the solid state,[24] it has
been shown to react with metal chlorides to generate metal
fluorides and volatile trimethyltin chloride.[23b,23c,25] Specifically,
Me3SnF has been used to prepare a variety of alkaline-earth
[a] Chemistry Division, Los Alamos National Laboratory,
Mailstop J-514, Los Alamos, New Mexico 87545, USA
E-mail: kiplinger@lanl.gov
[b] Department of Chemistry, University of Vermont,
Discovery Hall, Burlington, Vermont 05405, USA
[c] Materials Physics and Applications Division,
Los Alamos National Laboratory,
Mailstop J-514, Los Alamos, New Mexico 87545, USA
[d] Materials Science and Technology Division,
Los Alamos National Laboratory,
Mailstop E-549, Los Alamos, New Mexico 87545, USA
Supporting information and ORCID(s) from the author(s) for this article are
available on the WWW under https://doi.org/10.1002/ejic.201701232.
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(Mg,[26] Ca,[27] Sr[28]), early (Sc,[29] Y,[29] Ti,[23a,29,30] Zr,[23a,30h,31] N(1)–C(21) [170.0(2)°], F(1)–U(1)–N(1) [106.60(8)°], and CCent–U–
Hf,[23a,31b–31e] V,[32] Nb,[33] Ta[34]), mid (W[30j,35]), and late (Fe,[36] CCent [143.0(1)°] bond angles of 4 are also comparable to those
Co,[37] Zn[38]
) =
transition-metal, main-group (Al,[39] Ga,[39g] observed for (C5Me5)2U(F)(=N-2,4,6-tBu3C6H2) [U–N–CAr
Si,[23c,40] Ge,[41] Sb,[42] P[23b,43]) and lanthanide-metal (Sm,[44] 171.0(7)°, F–U–N = 97.0(3)°, and CCent–U–CCent = 132.1(2)°].[9b]
Ho,[29] Er[29]) organometallic and inorganic fluoride complexes.
In this contribution, we demonstrate for the first time the
use of Me3SnF in halide exchange reactions with a suite of orga-
nometallic and inorganic actinide chloride, bromide, and iodide
complexes as a mild route for the synthesis of thorium and
uranium fluoride complexes. We further show that this method-
ology does not seem to be limited by metal (thorium vs. ura-
nium), oxidation state [uranium(IV) vs. uranium(V)] or ligand
platform (metallocene vs. non-metallocene).
These values are also in agreement with those observed for the
chloride, bromide, and iodide analogues of (C5Me5)2U(X)-
(=N-2,6-iPr2C6H3).[9b]
Results and Discussion
Known uranium(V) imido halide complexes were chosen to ini-
tially examine the ability of Me3SnF to serve as a fluorinating
reagent for the preparation of organometallic actinide fluorides.
As shown in Equation (1), (C5Me5)2U(X)(=N-2,6-iPr2C6H3) [X = Cl
(1), Br (2), I (3)],[9a,9b] reacts with 2 equiv. of Me3SnF to afford
(C5Me5)2U(F)(=N-2,6-iPr2C6H3) (4).[12] The resulting Me3SnX (X =
Cl, Br, I) byproduct is easily removed under reduced pressure,
and the uranium(V) fluoride (4) is obtained in excellent yields
(79–98 %) following work up. If desired, the Me3SnX (X = Cl,
Br, I) can be subsequently converted back into Me3SnF by reac-
tion with aqueous KF solution.[24,36,45] When the reactions are
monitored by 1H NMR spectroscopy in [D6]benzene, resonances
corresponding to the uranium(V) imido halide complex (4), in
addition to singlets at δ = 0.29, 0.40, and 0.48, are observed for
Me3SnX (X = Cl, Br, and I), respectively, consistent with a halide
exchange reaction.[46] Previously, complex 4 was synthesized
by the oxidation of (C5Me5)2U(=N-2,6-iPr2C6H3)(THF) with excess
CuF2,[9b] whereas the current procedure is redox-neutral.
Figure 1. Molecular structure of (C5Me5)2U(F)(=N-2,6-iPr2C6H3) (4) with ther-
mal ellipsoids projected at the 50 % probability level. Hydrogen atoms have
been omitted for clarity.
To understand the generality of this fluorination method, the
reactivity of Me3SnF with tetravalent uranium metallocene and
non-metallocene ligand frameworks was tested. Reaction of
Me3SnF with the uranium(IV) aryloxide–chloride complex,
(C5Me5)2U(Cl)(O-2,6-iPr2C6H3) (5),[47] proceeds smoothly at room
temperature to afford Me3SnCl and the corresponding ura-
nium(IV) fluoride complex (C5Me5)2U(F)(O-2,6-iPr2C6H3) (6)[12] in
93 % yield [Equation (2)]. Likewise, treatment of the uranium(IV)
tris(aryloxide) iodide and tris(amide) chloride complexes,
U(I)(O-2,6-tBu2C6H3)3 (7)[48] and U(Cl)[N(SiMe3)2]3 (9),[49] with
Me3SnF forms U(F)(O-2,6-tBu2C6H3)3 (8)[50] and U(F)[N(SiMe3)2]3
(10)[51] in 53 % and 93 % yields, respectively [Equations (3) and
(4)]. Previously, all three complexes, 6, 8, and 10, were prepared
by redox or fluoride-atom abstraction oxidative methods.
Structurally characterized pentavalent uranium fluoride com-
plexes are rare. Brown, crystalline blocks of 4 were grown by
slow evaporation of a saturated toluene solution at ambient
temperature and analyzed. Single-crystal X-ray diffraction con-
firmed the existence of the U–F bond in complex 4 (Figure 1).
The molecular structure features a typical bent-metallocene
framework with the fluoride and imido ligands in the metallo-
cene wedge. The U(1)–F(1) [2.1280(17) Å], U(1)–N(1) [1.981(2) Å],
and U–CCent [2.453(3), 2.453(3) Å, cent = cyclopentadienyl cen-
troid] bond lengths of complex 4 are all comparable to those
reported for the structurally related uranium(V) imido fluoride
complex (C5Me5)2U(F)(=N-2,4,6-tBu3C6H2) [U–F = 2.122(5) Å,
U–N = 1.965(8) Å, U–CCent = 2.453(3), 2.453(3) Å].[9b] The U(1)–
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One interesting observation made during the course of these
Earlier work by our group showed that monometallic ura-
studies was that the liberated Me3SnCl and Me3SnI in reactions nium difluoride complex 15 could be prepared by protonolysis
2–4 can react with the uranium aryloxide and amide ancillary of (C5Me5)2UMe2 with Et3N·3HF in the presence of trimethyl-
linkages in (C5Me5)2U(F)(O-2,6-iPr2C6H3) (6), U(F)(O-2,6- phosphine oxide.[21] Halide exchange using Me3SnF not only
tBu2C6H3)3 (8) and U(F)[N(SiMe3)2]3 (10) to form the correspond- offers a higher yielding and more streamlined route to 15, but
ing trimethyltin derivatives Me3Sn(O-2,6-iPr2C6H3) [δ[D6]benzene
=
also enables access to the triphenylphosphine oxide (16) and
0.25 (SnCH3), 1.27 (iPr-CH3), 3.38 (iPr-CH), 6.93 (p-Ar–H), 7.12 tricyclohexylphosphine oxide (17) derivatives.
(m-Ar–H)], Me3Sn(O-2,6-tBu2C6H3) [δ[D6]benzene = 0.32 (SnCH3),
1.49 (tBu-CH3), 6.90 (p-Ar–H), 7.35 (m-Ar–H)], and
Me3SnN(SiMe3)2 [δ[D6]benzene = 0.21 (SiCH3), 0.25 (SnCH3)], re-
spectively, which were identified by monitoring the reactions
Complexes 16 and 17 represent new members to this small
but growing class of low-valent uranium fluorides. Similar to
complex 15, 19F NMR resonances were not visible for the termi-
nal fluoride ligands in either complex 16 or 17. The 1H NMR
spectrum for (C5Me5)2UF2(O=PPh3) (16) in [D6]benzene is sim-
1
by H NMR spectroscopy.[46] We found that this side reaction is
circumvented by immediately placing the reactions under re-
duced pressure after the Me3SnF is added such that volatile
Me3SnX (X = Cl, Br, I) compounds are removed as they are
formed.
Finally, additional studies were carried out to see if the
Me3SnF chemistry could be applied to not only the installation
of multiple fluoride bonds, but also as a fluorinating reagent at
actinide metal centers other than uranium. Indeed, the metallo-
cene thorium(IV) dichloride complex (1,2,4-tBu3C5H2)2ThCl2
(11)[52] reacts cleanly with 2 equiv. of Me3SnF, yielding (1,2,4-
tBu3C5H2)2ThF2 (12, 90 %)[15b] [Equation (5)]. Previously, com-
plex 12 was prepared by oxidation of the bipyridyl thorium
metallocene complex, (1,2,4-tBu3C5H2)2Th(bipy) (bipy = 2,2′-bi-
pyridine) using AgF.[15b]
As shown in Equation (6), similar chemistry was observed for
uranium. Reaction of the uranium(IV) dichloride and dibromide
complexes (C5Me5)2UX2 [X = Cl (13),[53] Br (14)[47]] in the pres-
ence of phosphine oxides afforded the monometallic difluoride
uranium(IV) complexes (C5Me5)2UF2(O=PR3) [R = CH3 (15, 97–
99 %);[21] R = Ph (16, 70–99 %); R = Cy (17, 71–77 %)]. Due to
the basicity of the fluoride ligand, a characteristic feature of
organometallic fluoride complexes is the tendency to form
fluoride bridges between two or more metal atoms. However,
the added phosphine oxide donor ligands help to sterically sat-
urate the uranium metal center and prevent dimer formation
in both the solution and solid state.
Figure 2. Molecular structures of (C5Me5)2UF2(O=PMe3) (15), (C5Me5)2UF2(O=
PPh3) (16), and (C5Me5)2UF2(O=PCy3) (17) with thermal ellipsoids projected
at the 50 % probability level. Hydrogen atoms have been omitted for clarity.
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couple using capillary tubes flame-sealed under N2; values are un-
corrected. Elemental Analyses were performed by ALS Environmen-
tal (Tucson, AZ) or Atlantic Microlab, Inc. (Norcross, GA).
ple and shows a singlet at δ = –2.47 ppm for the C5Me5 protons
and broad resonances at δ = 6.74 (m-Ar–H), 4.62 (p-Ar–H), and
2.60 (o-Ar–H) corresponding to the phenyl groups on the coor-
dinated Ph3P=O ligand. The 1H NMR spectrum for Materials: Unless otherwise noted, reagents were purchased from
commercial suppliers and used without further purification. Celite
(Aldrich), alumina (Brockmann I, Aldrich), and 3 Å molecular sieves
(Aldrich) were dried under dynamic vacuum at 250 °C for 48 h prior
to use. All solvents (Aldrich) were purchased anhydrous, dried with
KH for 48 h, passed through a column of activated alumina,
and stored over activated 3 Å molecular sieves prior to use.
(C5Me5)2U(X)(=N-2,6-iPr2C6H3) (X = Cl, Br, I),[9a,9b] (C5Me5)2U(Cl)-
(O-2,6-iPr2C6H3),[47] U(I)(O-2,6-tBu2C6H3)3,[55] U(Cl)[N(SiMe3)2],[49]
(C5Me5)2UCl2,[53] (C5Me5)2UBr2,[47] (1,2,4-tBu3C5H2)2ThCl2,[52] and
Me3SnF[36] were prepared according to literature procedures.
(C5Me5)2UF2(O=PCy3) (17) in [D6]benzene is a bit more compli-
cated with a singlet at δ = –1.81 ppm for the C5Me5 protons
and several broad resonances corresponding to the protons of
inequivalent cyclohexyl groups on the coordinated Cy3P=O
ligand. Finally, complexes (C5Me5)2UF2(O=PMe3) (15),
(C5Me5)2UF2(O=PPh3) (16) and (C5Me5)2UF2(O=PCy3) (17) in
[D6]benzene all display signals in their 31P{1H} NMR spectra at
δ = –34.76, –9.38, and 14.87, respectively.
The molecular structures of 15–17 are given in Figure 2. All
three complexes display bent metallocene structures with the
phosphine oxide coordinated to the uranium(IV) metal center
between two fluoride ligands within the wedge. The terminal
Synthesis of (C5Me5)2U(F)(=N-2,6-iPr2C6H3) (4)
Method A: From (C5Me5)2U(Cl)(=N-2,6-iPr2C6H3) (1): A 20-mL
scintillation vial was charged with a stir bar, (C5Me5)2U(Cl)(=N-2,6-
iPr2C6H3) (1, 0.300 g, 0.418 mmol), Me3SnF (0.153 g, 0.836 mmol),
and toluene (5 mL). The reaction mixture was stirred at ambient
temperature for 4 h and then the volatiles were removed under
reduced pressure. The resulting residue was dissolved in hexane
(15 mL) and filtered through a Celite-padded coarse-porosity fritted
filter. All volatiles were removed from the brown filtrate to give
(C5Me5)2U(F)(=N-2,6-iPr2C6H3) (4) as a brown solid (0.266 g,
0.378 mmol, 90 %). The 1H NMR spectrum collected in [D6]benzene
U–F bond lengths are 2.1285(12) and 2.1292(12)
Å for
(C5Me5)2UF2(O=PMe3) (15), 2.1223(32) and 2.1325(28) Å for
(C5Me5)2UF2(O=PPh3) (16), and 2.1277(17) and 2.1246(17) Å for
(C5Me5)2UF2(O=PCy3) (17). Although these values are similar to
that observed in the structurally related (C5Me5)2UF2(py) [U–F =
2.146(5) Å],[21] they are significantly longer than those reported
for the other known uranium(IV) terminal fluoride complexes
(1,2,4-tBu3C5H2)2UF2 [U–F = 2.081(5) Å],[18] (1,3-tBu2C5H3)2UF2
[U–F = 2.086(5) Å[17]], and Tp*2UF2 ([U–F = 2.086(6), 2.090(6) Å].
This observation is consistent with comparatively more elec-
tron-rich uranium metal centers in complexes 15–17 due to the
additional electron density provided by the phosphine oxide
ligands.
was consistent with data previously reported for complex 4.[9b] 1
H
NMR ([D6]benzene, 298 K): δ = 69.65 (s, 1 H, CHMe2), 26.08 (s, 1 H,
ν1/2 = 69 Hz, Ar–H), 16.76 (s, 1 H, ν1/2 = 28 Hz, Ar–H), 15.39 (s, 6 H,
ν1/2 = 66 Hz, CHMe2), 3.93 (s, 30 H, ν1/2 = 107 Hz, C5Me5), –10.11 (s,
6 H, ν1/2 = 48 Hz, CHMe2), –15.93 (s, 1 H, ν1/2 = 133 Hz, Ar–H), –34.99
(s, 1 H, CHMe2) ppm. Method B: From (C5Me5)2U(Br)(=N-2,6-
iPr2C6H3) (2): A 20-mL scintillation vial was charged with a stir bar,
(C5Me5)2U(Br)(=N-2,6-iPr2C6H3) (2, 0.220 g, 0.289 mmol), Me3SnF
(0.106 g, 0.578 mmol), and toluene (5 mL). The reaction mixture
was stirred at ambient temperature for 4 h and then the volatiles
were removed under reduced pressure. The resulting residue was
dissolved in hexane (15 mL) and filtered through a Celite-padded
coarse-porosity fritted filter. The brown filtrate was collected
and volatiles were removed under reduced pressure to give
(C5Me5)2U(F)(=N-2,6-iPr2C6H3) (4) as a brown solid (0.155 g,
0.221 mmol, 76 %). Method C: From (C5Me5)2U(I)(=N-2,6-iPr2C6H3)
(3): A 20-mL scintillation vial was charged with a stir bar,
(C5Me5)2U(I)(=N-2,6-iPr2C6H3) (3, 0.300 g, 0.371 mmol), Me3SnF
(0.136 g, 0.742 mmol), and toluene (5 mL). The reaction mixture
was stirred at ambient temperature for 4 h and then the volatiles
were removed under reduced pressure. The resulting residue was
dissolved in hexane (15 mL) and filtered through a Celite-padded
coarse-porosity fritted filter. The brown filtrate was collected
and volatiles were removed under reduced pressure to give
(C5Me5)2U(F)(=N-2,6-iPr2C6H3) (4) as a brown solid (0.260 g,
0.370 mmol, 99 %). Single crystals suitable for X-ray diffraction were
obtained by slow evaporation of a saturated toluene solution at
ambient temperature.
Conclusions
We have shown that trimethyltin fluoride (Me3SnF) serves as a
mild and selective reagent for the installation of actinide fluor-
ide bonds. The halide exchange reaction with actinide chloride,
bromide, and iodide complexes affords the corresponding fluor-
ides as demonstrated by the synthesis of a variety of organome-
tallic and inorganic thorium and uranium fluoride complexes.
As this chemistry does not seem to be limited by actinide metal,
oxidation state, or ligand platform, we expect that this protocol
will provide a general means for introducing fluoride ligands
on actinide metal centers.
Experimental Section
General Considerations: Unless otherwise noted, all reactions and
manipulations were performed at 20 °C in a recirculating Vacuum
Atmospheres NEXUS model inert atmosphere (Ar or N2) drybox
equipped with a 40CFM Dual Purifier NI-Train. Glassware was dried
overnight at 150 °C before use. NMR spectra were obtained using
Synthesis of (C5Me5)2U(F)(O-2,6-iPr2C6H3) (6): A 20-mL scintilla-
tion vial was charged with a stir bar, (C5Me5)2U(Cl)(O-2,6-iPr2C6H3)
a Bruker Avance 400 MHz spectrometer at ambient temperature.
Chemical shifts for H and 13C{1H} NMR spectra were referenced to (5, 0.100 g, 0.139 mmol), Me3SnF (0.025 g, 0.139 mmol), and toluene
1
solvent impurities.[54] 31P{1H} NMR spectra were referenced to an
external 85 % H3PO4 solution. IR spectra were obtained using a
Thermo Scientific Nicolet iS5 FT–IR spectrometer, using a Golden
Gate Diamond ATR (ZnSe lenses) with a reaction anvil (neat solid
(5 mL). The reaction mixture was immediately placed under reduced
pressure until dry. The reaction mixture was then charged with a
second equivalent of Me3SnF (0.025 g, 0.139 mmol) in toluene
(5 mL), and subsequently placed under reduced pressure until dry.
samples). Melting points were determined with a Mel-Temp II capil- The resulting residue was dissolved in toluene (5 mL) and filtered
lary melting point apparatus equipped with a Fluke 50S K/J thermo- through a Celite-padded coarse-porosity fritted filter. The red filtrate
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was collected and the volatiles were removed under reduced pres- ν = 2950, 2909, 2856, 1437, 1376, 1311, 1296, 1103, 944, 863, 779,
˜
sure to give (C5Me5)2U(F)(O-2,6-iPr2C6H3) (6) as a red solid (0.091 g,
752, 737, 545 cm–1. M.p. 227–229 °C. Single crystals suitable for X-
ray diffraction were obtained by upon cooling a saturated toluene
solution to –30 °C. Method B: From (C5Me5)2UBr2 (14): A 20-mL
scintillation vial was charged with a stir bar, (C5Me5)2UBr2 (14,
0.100 g, 0.150 mmol), O=PMe3 (0.014 g, 0.150 mmol), Me3SnF
(0.027 g, 0.150 mmol) and toluene (5 mL). The reaction mixture was
immediately placed under vacuum until dry. A second equivalent
of Me3SnF (0.027 g, 0.150 mmol) and toluene (5 mL) were added
and the reaction mixture was immediately placed under vacuum
until dry. The resulting residue was dissolved in toluene (5 mL) and
filtered through a Celite-padded coarse-porosity fritted filter. The
yellow filtrate was collected and the volatiles were removed under
reduced pressure to give (C5Me5)2UF2(O=PMe3) (15) as a yellow
solid (0.095 g, 0.149 mmol, 99 %).
0.129 mmol, 93 %). The 1H NMR spectrum collected in [D6]benzene
was consistent with data previously reported for complex 6.[12] 1
H
3
NMR ([D6]benzene, 298 K): δ = 6.75 (d, 1 H, JH,H = 8 Hz, m-Ar–H),
3
3
6.30 (t, 1 H, JH,H = 8 Hz, p-Ar–H), 4.13 (d, 1 H, JH,H = 8 Hz, m-Ar–
H), 3.19 (s, 30 H, C5Me5), –1.71 (s, 6 H, CHMe2), –10.25 (s, 1 H, CHMe2),
–11.45 (s, 6 H, CHMe2), –45.33 (s, 1 H, CHMe2) ppm.
Synthesis of U(F)(O-2,6-tBu2C6H3)3 (8): A 20-mL scintillation vial
was charged with a stir bar, U(I)(O-2,6-tBu2C6H3)3 (7, 0.084 g,
0.085 mmol), Me3SnF (0.016 g, 0.085 mmol), and THF (5 mL). The
reaction mixture immediately placed under reduced pressure until
dry. The resulting residue was triturated with (Me3Si)2O (3 mL). In-
soluble solids were collected on a coarse-porosity fritted filter,
washed with (Me3Si)2O (0.5 mL), and dried under reduced pressure
to give U(F)(O-2,6-tBu2C6H3)3 (8) as a yellow solid (0.040 g,
0.046 mmol, 54 %). The 1H NMR spectrum collected in [D6]benzene
Synthesis of (C5Me5)2UF2(O=PPh3) (16)
Method A: From (C5Me5)2UCl2 (13): A 20-mL scintillation vial was
charged with a stir bar, (C5Me)2UCl2 (13, 0.100 g, 0.172 mmol), O=
PPh3 (0.048 g, 0.172 mmol), Me3SnF (0.032 g, 0.172 mmol), and
toluene (5 mL). The reaction mixture was immediately placed under
vacuum until dry. The resulting residue was charged with Me3SnF
(0.032 g, 0.172 mmol) and toluene (5 mL). The reaction mixture was
immediately placed under vacuum until dry. The resulting residue
was dissolved in toluene (5 mL), filtered through a Celite-padded
coarse-porosity fritted filter. The yellow filtrate was collected and
the volatiles removed under reduced pressure to give (C5Me5)2-
was consistent with data previously reported for complex 8.[50] 1
H
NMR ([D6]benzene, 298 K): δ = 15.97 (s, 6 H, ν1/2 = 43 Hz, m-Ar–H),
12.43 (s, 3 H, ν1/2 = 28 Hz, p-Ar–H), –4.54 (s, 54 H, ν1/2 = 62 Hz,
CMe3) ppm.
Synthesis of U(F)[N(SiMe3)2]3 (10): A 20-mL scintillation vial was
charged with a stir bar, U(Cl)[N(SiMe3)2]3 (9, 0.100 g, 0.133 mmol),
Me3SnF (0.027 g, 0.146 mmol), and toluene (3 mL). The reaction
mixture was immediately placed under reduced pressure until dry.
The resulting residue was dissolved in hexane (5 mL) and filtered
through a Celite-padded coarse-porosity fritted filter. The purple
filtrate was collected and volatiles were removed under reduced
pressure to give U(F)[N(SiMe3)2]3 (10) as a purple solid (0.095 g,
0.129 mmol, 98 %). The 1H NMR spectrum collected in [D6]benzene
1
UF2(O=PPh3) (16) as a yellow solid (0.099 g, 0.120 mmol, 70 %). H
NMR ([D6]benzene, 298 K): δ = 6.74 (s, 6 H, ν1/2 = 16 Hz, m-Ar–H),
4.62 (s, 3 H, ν1/2 = 19 Hz, p-Ar–H), 2.60 (s, 6 H, ν1/2 = 37 Hz, o-Ar–
H), –2.47 (s, 30 H, ν1/2 = 32 Hz, C5Me5) ppm. 31P{1H} NMR ([D6]-
benzene, 298 K): δ = –9.38 ppm. IR (ATR-IR, 296 K, neat): ν = 3058,
˜
was consistent with data previously reported for complex 10.[51] 1
H
2901, 2854, 2721, 1486, 1436, 1376, 1147, 1120, 1089, 1072, 1027,
997, 896, 749, 723, 692, 535 cm–1. M.p. 239–240 °C. Elemental analy-
sis could not be obtained due to poor combustibility of the sample.
Single crystals suitable for X-ray diffraction were obtained upon
cooling a saturated toluene solution layered with hexane to –30 °C.
Method B: From (C5Me5)2UBr2 (14): A 20-mL scintillation vial was
charged with a stir bar, (C5Me)2UBr2 (14, 0.100 g, 0.150 mmol), O=
PPh3 (0.042 g, 0.150 mmol), Me3SnF (0.027 g, 0.150 mmol), and
toluene (5 mL). The reaction mixture was immediately placed under
vacuum until dry. The resulting residue was charged with Me3SnF
(0.027 g, 0.150 mmol) and toluene (5 mL). The reaction mixture
immediately placed under vacuum until dry. The resulting residue
was dissolved in toluene (5 mL) and filtered through a Celite-pad-
ded coarse-porosity fritted filter. The yellow filtrate was collected
and the volatiles removed under reduced pressure to give
(C5Me5)2UF2(O=PPh3) (16) as a yellow solid (0.123 g, 0.149 mmol,
99 %).
NMR ([D6]benzene, 298 K): δ = –4.57 (s, 36 H, ν1/2 = 479 Hz, SiMe3)
ppm.
Synthesis of (1,2,4-tBu3C5H2)ThF2 (12): A 20-mL scintillation vial
was charged with a stir bar, (1,2,4-tBu3C5H2)2ThCl2 (11, 0.085 g,
0.110 mmol), Me3SnF (0.040 g, 0.220 mmol, 2 equiv.), and toluene
(5 mL). The reaction mixture was immediately placed under vacuum
until dry. The resulting residue was dissolved in toluene (5 mL) and
filtered through a Celite-padded coarse-porosity fritted filter. The
yellow filtrate was collected and the volatiles were removed under
reduced pressure to give (1,2,4-tBu3C5H2)2ThF2 (12) as a white solid
(0.073 g, 0.100 mmol, 90 %). The 1H NMR spectrum collected in
[D6]benzene was consistent with data previously reported for com-
plex 12.[15b] 1H NMR ([D6]benzene, 298 K): δ = 6.35 (s, 4 H, CH), 1.55
(s, 36 H, CMe3), 1.37 (s, 18 H, CMe3) ppm.
Synthesis of (C5Me5)2UF2(O=PMe3) (15)
Synthesis of (C5Me5)2UF2(O=PCy3) (17)
Method A: From (C5Me5)2UCl2 (13): A 20-mL scintillation vial was
charged with a stir bar, (C5Me5)2UCl2 (13, 0.100 g, 0.172 mmol), O=
PMe3 (0.016 g, 0.172 mmol), Me3SnF (0.063 g, 0.344 mmol) and
toluene (5 mL). The reaction mixture was immediately placed under
Method A: From (C5Me5)2UCl2 (13): A 20-mL scintillation vial was
charged with a stir bar, (C5Me)2UCl2 (13, 0.200 g, 0.344 mmol), O=
PCy3 (0.102 g, 0.344 mmol), Me3SnF (0.063 g, 0.344 mmol), and
toluene (5 mL). The reaction mixture was immediately placed under
vacuum until dry. The resulting residue was dissolved in toluene vacuum until dry. The resulting residue was charged with Me3SnF
(5 mL) and filtered through a Celite-padded coarse-porosity fritted (0.063 g, 0.344 mmol) and toluene (5 mL). The reaction mixture was
filter. The yellow filtrate was collected and volatiles were removed
immediately placed under vacuum until dry. The resulting residue
under reduced pressure to give (C5Me5)2UF2(O=PMe3) (15) as a yel- was dissolved in toluene (5 mL), filtered through a Celite-padded
low solid (0.107 g, 0.167 mmol, 97 %). The 1H NMR spectrum col-
lected in [D6]benzene was consistent with data previously reported
for complex 15.[21] 1H NMR ([D6]benzene, 298 K): δ = –2.22 (s, 30 H,
coarse-porosity fritted filter. The yellow filtrate was collected and
the volatiles were removed under reduced pressure to give
(C5Me5)2UF2(O=PCy3) (17) as a yellow solid (0.224 g, 0.265 mmol,
2
1
ν1/2 = 32 Hz, C5Me5), –17.31 (d, 9 H, JP-H = 10 Hz, O=PMe3). 31P{1H}
77 %). H NMR ([D6]benzene, 298 K): δ = 7.97 (s, 6 H, ν1/2 = 51 Hz,
NMR ([D6]benzene, 298 K): δ = –34.76 ppm. IR (ATR-IR, 296 K, neat):
Cy-H), 2.10–1.88 (m, 3 H, Cy-H), –1.15 (s, 3 H, ν1/2 = 20 Hz, Cy-H),
Eur. J. Inorg. Chem. 0000, 0–0
www.eurjic.org
5
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
–1.81 (s, 30 H, ν1/2 = 34 Hz, C5Me5), –3.56 (s, 6 H, ν1/2 = 48 Hz,
Cy-H), –6.36 (s, 6 H, ν1/2 = 33 Hz, Cy-H), –10.74 (s, 6 H, ν1/2 = 32 Hz,
Cy-H), –32.42 (s, 3 H, ν1/2 = 36 Hz, Cy-H) ppm. 31P{1H} NMR ([D6]-
Acknowledgments
For financial support of this work, we acknowledge the U.S.
Department of Energy through the Los Alamos G. T. Seaborg
Institute for Transactinium Science (Undergraduate Student Fel-
lowship to B. D. K.; Postdoctoral Fellowships to A. G. L., K. A. E.,
and M. J. M.), the Los Alamos National Laboratory (Director and
Reines PD Fellowships to M. J. M.), the Office of Science, Office
of Workforce Development for Teachers and Scientists (WDTS)
under the Science Undergraduate Laboratory Internship (SULI)
program (Fellowship to B. D. K.), the Advanced Fuels Campaign
Fuel Cycle Research & Development Program (A. T. N.), and the
LANL LDRD Program. Los Alamos National Laboratory is oper-
ated by Los Alamos National Security, LLC, for the National Nu-
clear Security Administration (contract DE-AC52-06NA25396).
benzene, 298 K): δ = 14.87 ppm. IR (ATR-IR, 296 K, neat): ν = 2928,
˜
2850, 2176, 1444, 1343, 1286, 1228, 1130, 1095, 1075, 1049, 1026,
1005, 987, 953, 762, 563 cm–1. M.p. 260.5–262.5 °C. C38H63F2OPU
(842.91): C, 54.15; H, 7.53; found C, 53.13; H, 7.64. Single crystals
suitable for X-ray diffraction were obtained upon cooling a satu-
rated toluene solution to –30 °C. Method B: From (C5Me5)2UBr2
(14): A 20-mL scintillation vial was charged with a stir bar,
(C5Me)2UBr2 (14, 0.100 g, 0.150 mmol), O=PCy3 (0.044 g,
0.150 mmol), Me3SnF (0.027 g, 0.150 mmol), and toluene (5 mL).
The reaction mixture was immediately placed under vacuum until
dry. The resulting residue was charged with Me3SnF (0.027 g,
0.150 mmol) and toluene (5 mL). The reaction mixture immediately
placed under vacuum until dry. The resulting residue was dissolved
in toluene (5 mL), filtered through a Celite-padded coarse-porosity
fritted filter. The yellow filtrate was collected and the volatiles re-
moved under reduced pressure to give (C5Me5)2UF2(O=PCy3) (17)
as a yellow solid (0.089 g, 0.106 mmol, 71 %).
Keywords: Thorium · Uranium · Fluorides · Halides ·
Trimethyltin fluoride
X-ray Crystallography
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Data for (C5Me5)2U(F)(=N-2,6-iPr2C6H3) (4), (C5Me5)2UF2(O=PMe3)
(15), and (C5Me5)2UF2(O=PPh3) (16) were collected on a Bruker
Apex II diffractometer, with an APEX II CCD detector. Data for
(C5Me5)2UF2(O=PCy3) (17) were collected on a Bruker D8 Quest dif-
fractometer, with CMOS detector in shutterless mode. Data for
C
32H47FNU (4): monoclinic, P21/c, a = 12.927(2) Å, b = 11.4779(18) Å,
c = 19.746(3) Å, ꢀ = 91.802(2)°, V = 2928.4(8) Å3, Z = 4, ρ = 1.594 g/
cm3, μ = 5.569 Mo-Kα, T = 140 K, 2θmax = 57.24°, min/max trans. =
0.2391/0.4022, total reflns = 31885, unique reflns = 6677, parame-
ters = 330, R1 (wR2) [I ≥ 2σ(I)] = 0.0230(0.0607). Data for
C2 6. 5 H4 3 F2 OPU (15): monoclinic, P21 /c, a = 15.017(3) Å,
b = 10.962(2) Å, c = 16.779(3) Å, ꢀ = 90.1060(19)°, V = 2762.1(9) Å3,
Z = 4, ρ = 1.646 g/cm3, μ = 5.963 Mo-Kα, T = 140 K, 2θmax = 57.52°,
min/max trans. = 0.2513/0.5347, total reflns = 31594, unique
reflns = 6750, parameters = 398, R1(wR2) [I ≥ 2σ(I)] = 0.0165(0.0408).
Data for C45H53F2OPU (16): orthorhombic, P212121, a = 10.9732(8) Å,
b = 17.8607(13) Å, c = 20.5456(15) Å, ꢀ = 90.00°, V = 4026.7(5) Å3,
Z = 4, ρ = 1.512 g/cm3, μ = 4.112 Mo-Kα, T = 140 K, 2θmax = 53.62°,
min/max trans. = 0.4386/0.4935, total reflns = 40856, unique
reflns = 9618, parameters = 398, R1(wR2) [I ≥ 2σ(I)] = 0.0301(0.0723).
Data for C45H71F2OPU (17): monoclinic, P21/n, a = 10.4620(7) Å, b =
17.9494(13) Å, c = 22.8914(16) Å, ꢀ = 91.744(2)°, V = 4296.7(5) Å3,
Z = 4, ρ = 1.445 g/cm3, μ = 3.855 Mo-Kα, T = 140 K, 2θmax = 62.54°,
min/max trans. = 0.4116/0.5128, total reflns = 86771, unique
reflns = 14049, parameters = 398, R1 (wR2 ) [I ≥ 2σ(I)] =
0.0306(0.0954). The crystals were cooled with a Bruker KRYO-FLEX
liquid nitrogen vapor-cooling device (4, 15, 16), or an Oxford Cryo-
stream 700 (17). Hemispheres of data were collected with ω scans.
Data collection, initial indexing and cell refinements were handled
with APEX II software.[56] Frame integration, including Lorentz-polar-
ization corrections, and final cell parameter calculations were car-
ried out with Saint+ software.[57] The data were corrected for ab-
sorption with the SADABS program.[58] The structure was solved
with direct methods and difference Fourier techniques. Non-
hydrogen atoms were refined anisotropically and hydrogen atoms
were treated as idealized contributions. Structure solution and re-
finement were performed with SHELXTL.[59] CCDC 1572453 (for 16),
1572454 (for 4), 1572455 (for 17), and 1572456 (for 15) contain the
supplementary crystallographic data for this paper. These data can
be obtained free of charge from The Cambridge Crystallographic
Data Centre.
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Received: October 18, 2017
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© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
Fluorinating Reagents
Trimethyltin fluoride (Me3SnF) is a mild
and selective reagent for the installa-
tion of actinide fluoride bonds as dem-
onstrated by the room temperature
synthesis of a variety of organometal-
lic and inorganic thorium and uranium
from their corresponding chloride,
bromide, and iodide analogues.
B. D. Kagan, A. G. Lichtscheidl,
K. A. Erickson, M. J. Monreal,
B. L. Scott, A. T. Nelson,
J. L. Kiplinger* ..................................... 1–8
Synthesis of Actinide Fluoride Com-
plexes Using Trimethyltin Fluoride
as a Mild and Selective Fluorinating
Reagent
DOI: 10.1002/ejic.201701232
Eur. J. Inorg. Chem. 0000, 0–0
www.eurjic.org
8
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim