Reactivity of uranium(iii) with H2E (E = S, Se, Te): Synthesis of a series of mononuclear and dinuclear uranium(iv) hydrochalcogenido complexes

Article abstract of DOI:10.1039/c4sc02602k

We report the syntheses, electronic properties, and molecular structures of a series of mono- and dinuclear uranium(iv) hydrochalcogenido complexes supported by the sterically demanding but very flexible, single N-anchored tris(aryloxide) ligand (^AdArO)₃N)^3-. The mononuclear complexes [((^AdArO)₃N)U(DME)(EH)] (E = S, Se, Te) can be obtained from the reaction of the uranium(iii) starting material [((^AdArO)₃N)U^III(DME)] in DME via reduction of H₂E and the elimination of 0.5 equivalents of H₂. The dinuclear complexes [{((^AdArO)₃N)U}₂(μ-EH)₂] can be obtained by dissolving their mononuclear counterparts in non-coordinating solvents such as benzene. In order to facilitate the work with the highly toxic gases, we created concentrated THF solutions that can be handled using simple glovebox techniques and can be stored at -35 °C for several weeks. This journal is

Full text of DOI:10.1039/c4sc02602k

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Reactivity of uranium(III) with H E (E ¼ S, Se, Te):
2
synthesis of a series of mononuclear and dinuclear
Cite this: Chem. Sci., 2015, 6, 275
uranium(IV) hydrochalcogenido complexes†
Sebastian M. Franke, Michael W. Rosenzweig, Frank W. Heinemann
and Karsten Meyer*
We report the syntheses, electronic properties, and molecular structures of a series of mono- and dinuclear
uranium(IV) hydrochalcogenido complexes supported by the sterically demanding but very flexible, single
Ad
3ꢀ
Ad
N-anchored tris(aryloxide) ligand ( ArO)
3
N) . The mononuclear complexes [(( ArO)
3
N)U(DME)(EH)] (E
Ad
III
¼
S, Se, Te) can be obtained from the reaction of the uranium(III) starting material [(( ArO)
3
N)U (DME)]
2 2
in DME via reduction of H E and the elimination of 0.5 equivalents of H . The dinuclear complexes
Ad
Received 26th August 2014
Accepted 29th September 2014
[
3 2 2
{(( ArO) N)U} (m-EH) ] can be obtained by dissolving their mononuclear counterparts in non-
coordinating solvents such as benzene. In order to facilitate the work with the highly toxic gases, we
created concentrated THF solutions that can be handled using simple glovebox techniques and can be
DOI: 10.1039/c4sc02602k
ꢁ
www.rsc.org/chemicalscience
stored at ꢀ35 C for several weeks.
actinides are exceedingly rare. In fact, the only reported
Introduction
compound is the hydrosuldo complex [(Cp*)
3
U(SH)]
S or
Hydrochalcogenido complexes have received considerable (Cp* ¼ C
interest in transition metal chemistry due to their potential
applications as hydrodesulfurization and hydrogenation cata-
5
Me ) that was synthesized by Spirlet et al. from H
5
2
1–9
1,9–15
lysts, as well as their relevance in bioinorganic chemistry.
This class of compounds also serves as excellent precursors to a
variety of homo- and hetero-bimetallic chalcogenido clusters
9
,16–25
with high nuclearity,
optical properties.
some of which exhibit interesting
Furthermore, hydrochalcogenides have
2
6,27
shown unusual reactivity such as Michael-type addition reac-
tions with activated alkenes to afford the respective chalcoge-
19,28,29
nolato complexes.
In actinide chemistry, reports on
chalcogenido complexes in general are rather scarce compared
30–48
to the transition metals.
Nevertheless, there has been a
tremendous recent increase of interest in these types of
compounds, which is motivated by the academic interest in
synthesizing novel uranium–chalcogenide compounds and the
fundamental importance of understanding the nature of cova-
lent bonding between hard uranium ions and the so chalco-
49–52
genido ligands.
In contrast to their transition metal
chemistry, heavier main group 6 hydrochalcogenides of the
Department of Chemistry and Pharmacy, Inorganic Chemistry, Friedrich-Alexander
University of Erlangen-N u¨ rnberg (FAU), Egerlandstraße 1, D-91058 Erlangen,
Germany. E-mail: karsten.meyer@fau.de; Fax: +49 9131 8527367; Tel: +49 9131
8
527360
†
Electronic supplementary information (ESI) available: Full synthetic and
1
experimental details, spectroscopic data for H NMR, SQUID and UV/vis and
detailed X-ray crystallographic data in CIF format. CCDC 1020771–1020776. For
ESI and crystallographic data in CIF or other electronic format see DOI:
Chart 1 Complex formulas and numbering scheme of uranium
complexes 1-EH and 2-EH (E ¼ S, Se, Te), employing the chelating N-
Ad
3ꢀ
anchored ligand ( ArO)
3
N
(top).
1
0.1039/c4sc02602k
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in a salt metathesis reaction from [(Cp*)
no crystallographic evidence was provided.
3
U(Br)] and NaSH, but concentrated DME solution yielded crystals suitable for X-ray
53
diffraction analysis. The solid state structure of 1-SH reveals a
Ad
Herein, we report the synthesis of the rst series of uranium mononuclear complex [(( ArO) N)U(DME)(SH)] with a seven-
3
hydrochalcogenido complexes that can be obtained as mono- coordinate uranium center in a distorted, monocapped trigonal
Ad
nuclear complexes [(( ArO)
3
N)U(DME)(EH)] (1-EH, E ¼ S, Se, prismatic coordination environment, in which one molecule of
Ad
Te) or as dinuclear complexes [{(( ArO)
3
N)U}
2
(m-EH)
2
] (2-EH, E DME is coordinated to the uranium center in a bidentate
˚
¼
S, Se, Te) depending on the choice of solvent (Chart 1). In this fashion (Fig. 1, le). The U–S bond distance of 2.797(1) A is
manner, either 1-EH or 2-EH can be synthesized from the ura- clearly longer than reported U]S double bonds (2.382(11)–
Ad
˚
nium(III) starting material [(( ArO)
H E and the elimination of 0.5 equivalents of H .
3
N)U(DME)] via reduction of 2.481(1) A) and is in good agreement with a U–S single bond
˚
58,59,61–65
(2.588(1)–2.907(3) A, Table 1).
Furthermore, the chal-
2
2
cogen-bound hydrogen could be located in the difference
Fourier map and was subsequently treated using a riding
Results and discussion
˚
model. The U–N distance of 2.616(2) A and the U–Oavg. bonds of
˚
2
.171 A are comparable to other complexes supported by the
Recently, we reported the synthesis of the uranium(III) complex
Ad
3ꢀ 54,58,59
ꢀ
Ad
N-anchored ligand ( ArO) N
.
Additionally, the SH
3
[
3
(( ArO) N)U(DME)] supported by the exible, N-anchored
Ad
3ꢀ
Ad
3ꢀ
ligand is not coordinated in the axial position directly trans to
the nitrogen anchor, which is clearly shown in the N–U–S bond
chelator ( ArO) N (with ( ArO) N ¼ tris(2-hydroxy-3-ada-
3
3
54
mantyl-5-methylbenzyl)amine).
This reactive, low-valent
ꢁ
angle of 136.24(4) .
complex can undergo reactions such as the activation of CO
and its heterocumulene analogs COS and CS
2
5
5–57
Applying a similar synthetic procedure, the mononuclear
2
,
as well as the
Ad
58
selenolato complex [(( ArO) N)U(DME)(SeH)] (1-SeH) can be
3
activation of elemental chalcogens. The starting material
Ad
synthesized in 72% yield (Scheme 1). The molecular structure of
-SeH, obtained from crystals grown from a concentrated DME
[(( ArO)
3
N)U(DME)] exhibits a half-step potential of ꢀ1.879 V
1
for the uranium(III/IV) redox couple (see ESI†), supporting the
fact that this complex is a potent reductant, which – in part –
solution, compares well to that of 1-SH (Fig. 1, center). Note-
worthy, the asymmetric unit of the cell in 1-SeH contains two
independent but structurally very similar molecules of the
complex, and hence, only the values of 1-SeH A are given in
Table 1 (for more details see ESI†). According to the 3s criterion,
explains its observed reactivity with the H E substrates.
2
Furthermore, even uranium(IV) complexes supported by the
Ad
3ꢀ
(
ArO) N ligand can show remarkable reactivity under the
3
right conditions, such as the formation of polychalcogenido
complexes through stepwise addition of stoichiometrically
precise amounts of elemental chalcogen.
˚
˚
the U–N (2.605(3) A) and U–O
bond lengths (2.170 A) are the
avg.
˚
5
9
same as those observed in 1-SH. The U–Se bond of 2.936(1) A is
2
H S and its heavier
signicantly longer than a distinctive U]Se double bond
congeners H Se and H Te are known and well-documented
2
2
˚
(
2.533(1)–2.646(1) A) and can be compared to other complexes
precursors for the synthesis of hydrochalcogenides, however,
the resultant hydrochalcogenides are rarely stable compounds
and subsequent reactions oen lead to the formation of metal
polychalcogenide clusters or binary metal salts instead.
Furthermore, synthetic work is greatly complicated by the high
toxicity and malodor of these gases. With the commercial
with U–Se single bond distances varying from 2.719(1) to
3
.125(1) A˚ .
57–59,61–63,66,67
As in complex 1-SH, the N–U–Se angle is
ꢁ
1
,9
strongly bent with 133.44(7) . In contrast to 1-SH, the selenium-
bound hydrogen could not be located in the difference Fourier
map, but was conrmed in H and H{ H} NMR experiments.
1
2
1
1
5
The H NMR spectrum of 1-SeH recorded in pyridine-d shows a
2
availability of H S as a solution in THF, reactions with this gas
total of ten signals, ranging from ꢀ63 to 11 ppm, however, the
can be carried out under much simpler conditions. That said,
no such reagents exist for its selenium and tellurium analogs.
To solve these synthetic challenges, we created concentrated
solutions of H Se and H Te by condensing the respective gas
unambiguous assignment of the hydrogen resonance of the
ꢀ
SeH ligand is severely hampered due to the complicated
nature of the supporting ligand system. As a result, the
2
2
Ad
deuterated analog of 1-SeH, namely [(( ArO) N)U(DME)(SeD)]
3
formed from Al E (E ¼ Se, Te) and sulfuric acid into a THF
2
3
ꢁ
60
(1-SeD), was synthesized in a reaction of the uranium(III) start-
solution at ꢀ70 C. These solutions can be stored under an
Ad
1
ꢁ
ing material [(( ArO) N)U(DME)] with D Se. As expected, the H
3 2
inert atmosphere in a freezer at ꢀ35 C for several weeks. This
NMR spectrum of 1-SeD shows only nine signals, and thus,
2 2
procedure greatly simplies handling H Se and H Te.
ꢀ
unequivocally designates the signal at ꢀ62.86 ppm to the SeH
2
1
hydrogen. Additional H{ H} NMR experiments in pyridine
Synthesis and molecular structures of mononuclear
uranium(IV) hydrochalcogenido complexes 1-EH (E ¼ S, Se, Te)
revealed a single deuterium signal at ꢀ62.69 ppm that origi-
ꢀ
1
nates from the SeD moiety, further supporting the previous
Ad
The mononuclear thiolato complex [(( ArO)
3
N)U(DME)(SH)] assignment in the H NMR spectrum and conrming the
(
1-SH) has been synthesized by reacting the uranium(III) starting presence of the chalcogen-bound hydrogen.
Ad
material [(( ArO)
S via dropwise addition of a solution of H
reaction mixture turned green. Within ve minutes, a light [(( ArO)
green precipitate formed and 1-SH was obtained in 70% yield tions, since H
3
N)U(DME)] in THF with an excess amount of
In contrast to the closely related syntheses of 1-SH and
H
2
2
S in THF until the 1-SeH, the preparation of the tellurium analog complex
Ad
3
N)U(DME)(TeH)] (1-TeH), requires special precau-
2
Te is very susceptible to light and quickly
ꢁ
aer ltration and drying of the solids in vacuo (Scheme 1). decomposes at temperatures above 0 C. As a consequence, the
Recrystallization of the solid via diffusion of n-hexane into a reaction needs to be carried out in cooled solvents under the
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Scheme 1 Synthesis of hydrochalcogenido complexes 1-EH (E ¼ S, Se, Te).
rigorous exclusion of light to obtain 1-TeH in 78% yield U(DME)} (m-O)]. The reason why H O reacts so slowly with the
2
2
(
Scheme 1). Remarkably, the resulting complex 1-TeH is both uranium(III) starting material may be ascribed to the high
ꢁ
stable at elevated temperatures up to 80 C and in the presence stability of the O–H bond compared to the decreasingly stable
of light, which contrasts with the very few reported, usually E–H bonds in the hydrides of the heavier chalcogens.
rather unstable, transition metal complexes featuring a TeH
68
ꢀ
1,9
ligand. Single crystals suitable for X-ray diffraction were Synthesis and molecular structures of dinuclear uranium(IV)
obtained via diffusion of n-hexane into a mixture of benzene hydrochalcogenido complexes 2-EH (E ¼ S, Se, Te)
and DME (7 : 3). The molecular structure of 1-TeH is distinctly
Interestingly, crystallization of 1-EH from non-coordinating
different from those of 1-SH and 1-SeH, as it shows a six-coor-
solvents, such as benzene, leads to a change in coordination
geometry. X-ray diffraction analysis on crystals grown from
diffusion of n-hexane into saturated solutions of the complexes
dinate uranium center, located in a distorted octahedral coor-
dination environment (Fig. 1, right). Furthermore, and
consequently, the DME solvent molecule is now coordinated in
in benzene revealed the molecular structures of the dinuclear
˚
a monodentate fashion. The U–N (2.575(1) A) and U–Oavg. bond
Ad
complexes [{(( ArO) N)U} (m-EH) ] (E ¼ S, 2-SH; Se, 2-SeH; Te,
3
2
2
˚
lengths (2.130 A) are slightly shorter than those observed in
1
accordance with the formulation of a U–Te single bond
2
-TeH) (Scheme 2, Fig. 2). Each uranium center in 2-SH is now
˚
-SH and 1-SeH. The U–Te bond distance of 3.122(1) A is in
only six-coordinate and adopts a distorted octahedral coordi-
nation geometry. The U–S bond distances of 2.878(1)–2.964(1) A˚
are slightly longer than in 1-SH and are signicantly longer than
those observed in the dinuclear bis-m-suldo complex
5
8,61,62,67
ꢀ
(Table 1).
The TeH ligand is coordinated almost linearly
trans to the N-anchor in the axial position and shows a N–U–Te
angle of 173.25(4) . Attempts to obtain the hydroxo complex
ꢁ
Ad
˚
[
Na(DME) ] [{(( ArO) N)U} (m-S) ] (2.688(2)–2.714(2) A) or the
3 2 3 2 2
Ad
[(( ArO)
3
N)U(DME)(OH)] from H
2
O in the same way as
2
2
bridging persuldo complexes [{(R N) U} (m-h :h -S )] (R ¼
2
3
2
2
complexes 1-EH lead to the formation of the bridging oxo
species [{(( ArO)
presence of an excess amount of water. The rate of forming the
hydroxo complex [(( ArO)
2
2
˚
SiMe , 2.706(2)–2.923(2) A) and [{((SiMe NPh) tacn)U} (m-h :h -
3
2
3
2
Ad
54
3
N)U(DME)}
2
(m-O)] instead, even in the
˚
58,63,69
ꢀ
S
2
)] (2.855(2)–2.907(3) A).
The SH ligands with the shorter
U–S distances are now coordinated in the axial positions trans to
the nitrogen anchors, which is clearly visible in the N–U–S bond
Ad
3
N)U(DME)(OH)] appears to be much
Ad
slower than the subsequent reaction to form [{(( ArO) N)-
ꢁ
ꢁ
3
˚
angles of 166.14(4) and 166.63(4) . The U–Oavg. (2.121 A, 2.122
Fig. 1 Molecular structures of uranium hydrosulfido complex 1-SH (left), uranium hydroselenido complex 1-SeH (center), and uranium
hydrotellurido complex 1-TeH (right). The chalcogen-bound H atoms in 1-SH and 1-TeH could be located in the difference Fourier map, the
hydrogen in 1-SeH was placed in a position of optimized geometry. All other H atoms, the adamantyl groups, and co-crystallized solvent
molecules are omitted for clarity. Thermal ellipsoids are at 50% probability.
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Table 1 Selected bond distances ( A˚ ) and angles ( ) for complexes 1-EH and 2-EH (E ¼ S, Se, Te)
Edge Article
ꢁ
Structural parameters
1-SH
1-SeH
1-TeH
2-SH
2-SeH
2-TeH
U–Oavg.
U–ODME
U–N
2.169
2.170
2.130
2.121, 2.122
—
2.546(2), 2.542(2)
2.882(1), 2.961(1)
2.964(1), 2.877(1)
166.14(4), 87.79(4),
2.120, 2.122
—
2.119, 2.136
—
2.582(2) 2.616(2)
2.616(2)
2.797(1)
—
2.579(3) 2.599(3)
2.605(3)
2.936(1)
—
2.508(2)
2.575(2)
3.122(1)
—
2.552(3), 2.547(3)
2.992(1), 3.090(1)
3.094(1), 2.989(1)
168.44(6), 87.25(6),
88.23(6), 169.00(6)
158.10
2.558(3), 2.567(3)
3.145(2), 3.296(2)
3.163(2), 3.119(2)
171.00(7), 87.43(8),
94.94(9), 166.68(10)
160.09
U
U
1
–E1,2
–E1,2
2
N–U–E
136.24(4)
133.44(7)
173.25(4)
88.57(5), 166.63(4)
U–E
/E
/U
2
–U
—
—
—
—
—
—
—
—
—
159.99
3.888
4.295
E
U
1
2
4.157
4.381
4.479
4.448
1
2
ꢀ
˚
˚
˚
A) and U–N bond distances (2.546(1) A, 2.542(2) A) are in good as well as the oen highly nucleophilic EH functional groups
agreement with the respective structural parameters in show a strong tendency to form dinuclear species, hence, it is
complexes 1-EH (E ¼ S, Se, Te). As in complexes 1-SH and 1-TeH, within expectation that 1-EH can dimerize to 2-EH in non-
the chalcogen-bound hydrogens in complex 2-SH were located coordinating solvents, such as benzene, with the loss of coor-
1,54–59
in the difference Fourier map.
dinating solvent.
This conclusion is further supported by
The heavier chalcogenido complexes 2-SeH and 2-TeH the presence of broadened signals at approximately 3 ppm in all
exhibit the same molecular structures as 2-SH and feature spectra, which are attributed to uncoordinated DME. Likewise,
comparable U–Oavg. and U–N bond lengths (see Table 1). The the dinuclear species 2-EH dissociates in DME to form the
˚
U–Se and U–Te bonds range from 2.989(1) to 3.094(1) A and mononuclear complexes 1-EH.
˚
3
.119(2) to 3.296(2) A, respectively, which is slightly longer
compared to the bis-m-chalcogenido complexes [Na(DME) ] -
3
2
Infrared spectroscopy of complexes 1-EH and 2-EH
Ad
˚
[
{(( ArO) N)U} (m-E) ] (E ¼ Se, Te) (2.819(1)–2.866(1) A for
3
2
2
IR spectroscopy can be a useful tool to determine the presence
of an EH group, since the characteristic, but oen rather weak
IR-active n(E–H) bands usually appear in the regions between
˚
E ¼ Se and 3.031(1)–3.112(1) A for E ¼ Te) and the bridging
Ad
2
2
3 2
perselenido complex [{(( ArO) N)U} (m-h :h -Se)(m-DME)]
58,59
˚
(
1
1
2.942(1)–3.079(1) A).
Furthermore, the N–U–E angles of
ꢀ
1
70–76
ꢀ1
74–82
2
2
300–2600 cm (SH),
2200–2500 cm (SeH),
and 1800–
ꢁ
ꢁ
ꢁ
68.44(6) and 169.00(6) (2-SeH), as well as 171.00(7) and
ꢀ
1
74,76,83
000 cm (TeH).
However, complexes 1-SH and 2-SH, as
ꢁ
66.68(10) (2-TeH) are very similar compared to 2-SH but are
well as 1-SeH, 1-SeD and 2-SeH, do not show any n(E–H) bands at
slightly less bent due to a greater distance between the uranium
all, a fact that was also observed in several transition metal
˚
˚
˚
centers (d(U/U) ¼ 4.296 A (2-SH) < 4.381 A (2-SeH) < 4.448 A (2-
TeH)), which is in accordance with the larger atomic radii of
selenium and tellurium that lead to slightly higher steric
repulsion within the complexes. Noteworthy, the mononuclear
complexes 1-EH and their dinuclear counterparts 2-EH showed
15,18,84–90
complexes.
In contrast to this, complexes 1-TeH and 2-
ꢀ
1
TeH both show one distinctive absorption band at 2000 cm
ꢀ1
and 1998 cm , respectively, which is well in accordance with
the scarce amount of data available for hydrotellurido
complexes. Nevertheless, we could unambiguously identify the
H atoms in all complexes 1-EH and 2-EH via X-ray diffraction
1
identical H NMR spectra in deuterated benzene. Complexes
supported by the highly exible N-anchored ligand ( ArO) N
Ad
3ꢀ
3
2
1
analysis and H{ H} NMR spectroscopic experiments.
Scheme 2 Synthesis of dinuclear hydrochalcogenido complexes 2-EH (E ¼ S, Se, Te).
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Fig. 2 Molecular structures of uranium hydrosulfido complex 2-SH (top), uranium hydroselenido complex 2-SeH (bottom left), and uranium
hydrotellurido complex 2-TeH (bottom right). The chalcogen-bound H atoms in 2-SH, 2-SeH, and 2-TeH could be located in the difference Fourier
map. AllotherHatoms, theadamantylgroupsandco-crystallizedsolventmoleculesareomittedforclarity. Thermalellipsoidsareat50%probability.
UV/vis/NIR spectroscopy of complexes 1-EH and 2-EH
than those in complexes 1-EH. This observation is indicative of
weaker U–E bonds and lower covalency and is further supported
by the longer U–E bonds in the molecular structures of
The vis/NIR spectra of complexes 1-EH, recorded in DME, are all
very similar and show a number of low-intensity f–f transitions
92,93
ꢀ1
ꢀ1 complexes 2-EH.
Furthermore, in contrast to complexes
with small molar extinction coefficients of 10–35 M cm
between 500 and 2200 nm (see Fig. 3, le), characteristic for
1-EH, no hypsochromic shi was observed for any of the
91
complexes 2-EH, however, 2-SH and 2-SeH exhibit an additional
charge-transfer band at 395 and 406 nm, respectively (1-SH, 3 ¼
tetravalent complexes of uranium. While the spectra of 1-SH
and 1-SeH are almost identical, the spectrum of 1-TeH clearly
shows the hypsochromic shi of two bands at 1011 nm (3 ¼ 24
ꢀ
1
ꢀ1
ꢀ1
ꢀ1
2
185 M cm ; 1-SeH, 3 ¼ 2455 M cm ), that could not be
ꢀ
1
ꢀ1
ꢀ1
ꢀ1
observed for 2-TeH. The spectra of compounds 1-EH and 2-EH
M
cm ) and 1815 nm (3 ¼ 20 M cm ). This observation can
are indicative for tetravalent uranium centers and are in contrast
be rationalized by the discrepancy in the ligand-eld splitting
that should be expected due to the structural difference of 1-TeH
compared to 1-SH and 1-SeH. The UV/vis region shows one
intense charge-transfer band centered at 287 nm for each
1
3
91,94–97
to the spectra anticipated for a U(V) 5f or a U(III) 5f species.
Magnetism of complexes 1-EH and 2-EH
compound with molar extinction coefficients ranging from 14– The oxidation states and electronic structures of the uranium
3
ꢀ1
ꢀ1
1
9 ꢂ 10 M cm (see ESI, Fig. S25†). The electronic absorption centers in complexes 1-EH and 2-EH (E ¼ S, Se, Te) were further
spectra of complexes 2-EH, recorded in benzene, are all very characterized by temperature-dependent magnetic suscepti-
similar as well, showing very weak f–f transitions from 480 to bility measurements. SQUID magnetization measurements
ꢀ
1
ꢀ1
2
000 nm (3 ¼ 5–32 M cm , Fig. 3, right) and intense charge- from 2–300 K of compounds 1-EH all reveal very similar
transfer absorptions centered at 284 nm in the UV/vis region (3 ¼ magnetic moments of 2.56 (1-SH), 2.60 (1-SeH), and 2.60 B.M.
3
ꢀ1
ꢀ1
1
2–14 ꢂ 10 M cm , see ESI, Fig. S27†). For a better compar- (1-TeH) at 300 K, which decrease with decreasing temperature
ison, the molar extinction coefficients for complexes 2-EH were to 0.30 (1-SH), 0.30 (1-SeH), and 0.26 B.M. (1-TeH) at 2 K (Fig. 4,
calculated per uranium center, resulting in much lower values top). Likewise, the dinuclear complexes 2-EH show magnetic
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Fig. 3 Vis/NIR spectra of hydrochalcogenido complexes 1-SH (9.2 mM, black), 1-SeH (9.7 mM, red), and 1-TeH (4.1 mM, blue) recorded in DME at
ꢁ
2
5 C (left) and vis/NIR spectra of hydrochalcogenido complexes 2-SH (2.0 mM, black), 2-SeH (6.6 mM, red), and 2-TeH (6.5 mM, blue) recorded
ꢁ
in benzene at 25 C (right). The molar extinction coefficients for complexes 2-EH were calculated per uranium center for a better comparison.
is the difference in the plot of cM vs. T of 1-EH and 2-EH. While
the mononuclear complexes 1-EH show temperature-indepen-
dent paramagnetism (TIP) over a wide temperature range from
10 to 62 K (for 1-SH and 1-SeH) and 101 K (1-TeH), followed by a
steady decrease of the molar susceptibility, this feature is
slightly less pronounced in the dinuclear complexes 2-SH and
2-SeH (TIP below 50 K, see ESI†) and shows a signicant
difference in 2-TeH (TIP below 55 K).
Conclusion
The reaction of H
2
E (E ¼ S, Se, Te) with a reducing metal center
is a viable synthetic route to obtain metal hydrochalcogenido
complexes, however, handling of these gases is greatly compli-
cated due to their high toxicity. With the use of concentrated
and cooled solutions of these gases in THF, we were able to
synthesize the new uranium(IV) hydrochalcogenido complexes
Ad
[
(( ArO) N)U(DME)(EH)] (1-EH, E ¼ S, Se, Te), using simple
3
glovebox techniques. These compounds yield the dinuclear
complexes [{(( ArO)
coordinating solvents, such as benzene, with the loss of coor-
dinating DME. UV/vis/NIR spectroscopy and SQUID magneti-
zation measurements further conrm that complexes 1-EH and
Ad
3
N)U}
2
(m-EH)
2
] (2-EH, E ¼ S, Se, Te) in non-
2-EH can be clearly distinguished both in solution and in the
solid state. We are currently trying to access terminal mono-
chalcogenido species from the herein presented hydro-
chalcogenido complexes, in order to establish a series of chal-
cogenido complexes with U–E single and U]E double bonds
Fig.
4 Temperature-dependent SQUID magnetization data of
hydrochalcogenido complexes 1-EH (top, E ¼ S (black), Se (red), Te
(
blue)) and 2-EH (bottom, E ¼ S (black), Se (red), Te (blue)) as a plot of with similar coordination environments. This series should
m
eff vs. T. Data were corrected for underlying magnetism.
provide an excellent opportunity to gain more insight into the
covalency and f-orbital participation of the U–E bond in
uranium chalcogenido complexes.
moments of 2.46 (2-SH), 2.65 (2-SeH), and 2.44 B.M. (2-TeH) at
00 K that decrease to 0.34 (2-SH), 0.33 (2-SeH), and 0.31 B.M.
3
Acknowledgements
(2-TeH) at 2 K (Fig. 4, bottom). These observations are in
agreement with tetravalent uranium centers with a non- This work was supported by funds from the German Federal
3
58,98,99
magnetic H
4
ground state.
An interesting feature to note, Ministry of Education and Research (support codes 02 NUK
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12C and 02 NUK 020C). We greatly thank Alexander F. R. Kil- 28 F. Takagi, H. Seino, M. Hidai and Y. Mizobe, J. Chem. Soc.,
7
7
125
2
patrick and Dr. Andreas Scheurer for performing Se, Te, H
Dalton Trans., 2002, 3603–3610.
1
{
H}, and COSY NMR experiments. We would also like to thank 29 F. Takagi, H. Seino, Y. Mizobe and M. Hidai, Can. J. Chem.,
Dr. A. K. Abdul-Sada and Prof. Geoffrey N. Cloke for performing
2001, 79, 632–634.
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