R. K. Thomson, C. R. Graves, B. L. Scott, J. L. Kiplinger
SHORT COMMUNICATION
125-mL side-arm flask equipped with a stir bar was charged with
(C5Me5)2U(O-2,6-iPr2-C6H3)(THF) (1) (0.253 g, 0.33 mmol) and
toluene (40 mL). To the stirring deep green solution was added
solid (Ph3P)Au-N3 (0.167 g, 0.33 mmol), resulting in an immediate
color change to dark red. The solution was stirred at room tem-
perature for 12 h, filtered through a Celite-padded coarse-porosity
filter (Celite pad was washed with toluene until the washings were
colorless, ca. 10 mL), filtrate collected and volatiles removed under
reduced pressure to give a dark red solid residue. This solid was
dissolved in hexanes (20 mL), filtered through a Celite-padded
coarse-porosity filter (washed with hexanes until the washings were
colorless, ca. 10 mL), filtrate collected, and volatiles removed under
reduced pressure to give (C5Me5)2U(O-2,6-iPr2-C6H3)(N3) (9) as a
red-orange crystalline solid (0.190 g, 0.26 mmol, 78%). 1H NMR
(300 MHz, [D6]benzene, 25 °C): δ = 7.69 (d, J = 8 Hz, 1 H, m-Ar-
H), 7.00 (d, J = 8 Hz, 1 H, m-Ar-H), 6.59 (t, J = 8 Hz, 1 H, p-Ar-
H), 6.05 (s, 30 H, C5Me5), –5.56 (d, J = 4 Hz, 6 H, iPr-CH3), –13.18
(s, 6 H, iPr-CH3), –32.60 (m, 1 H, iPr-CH), –49.03 (m, 1 H, iPr-
CCDC-714038 (for 2), -714039 (for 5), -714040 (for 8), and -714041
(for 9) contain the supplementary crystallographic data for
this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
Acknowledgments
For financial support of this work, we acknowledge the Los
Alamos National Laboratory LDRD Program and G. T. Seaborg
Institute (Postdoctoral Fellowships to R. K. T. and C. R. G.), Los
Alamos National Laboratory (Director’s Postdoctoral Fellowship
to C. R. G.), and the Division of Chemical Sciences, Office of Basic
Energy Sciences, Heavy Element Chemistry program. The authors
thank Dr. Anthony E. Vaughn for executing preliminary reactions.
[1] A. S. K. Hashmi, Chem. Rev. 2007, 107, 3180–3211, and refer-
ences therein.
CH) ppm. IR (Nujol): ν = 2086 cm–1. M.p. 238–242 °C.
˜
[2] A. Li, C. Brouwer, C. He, Chem. Rev. 2008, 108, 3239–3265,
1H NMR Experiment for the Reaction of (C5Me5)2U(O-2,6-iPr2-
C6H3)(THF) (1) with (Ph3P)Au-CF3: A [D6]benzene (ca. 0.5 mL)
solution of (Ph3P)Au-CF3 (0.035 g, 0.066 mmol) was added by pi-
pette with stirring to a 20 mL scintillation vial charged with
(C5Me5)2U(O-2,6-iPr2-C6H3)(THF) (1) (0.050 g, 0.066 mmol) and
[D6]benzene (ca. 1 mL) at room temperature, resulting in an imme-
diate color change from dark green to a dark red solution. Analysis
by 1H NMR revealed complete conversion to complex (C5Me5)2-
U(O-2,6-iPr2-C6H3)(F) (5). 1H NMR (300 MHz, [D6]benzene,
25 °C): δ = –45.33 (br, 1 H, CHMe2), –11.45 (s, 7 H, CHMe2,
CHMe2), –1.71 (s, 6 H, CHMe2), 3.19 (s, 30 H, C5Me5), 4.13 (d, J
= 8 Hz, 1 H, m-Ar-H), 6.30 (t, J = 8 Hz, 1 H, p-Ar-H), 6.75 (d, J
= 8 Hz, 1 H, m-Ar-H) ppm.
and references therein.
[3] a) M. Contel, M. Stol, M. A. Casado, G. P. M. van Klink,
D. D. Ellis, A. L. Spek, G. van Koten, Organometallics 2002,
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A. L. Spek, G. P. M. van Klink, G. van Koten, Dalton Trans.
2007, 2589–2593; c) M. Ferrer, L. Rodriguez, O. Rossell, J. C.
Lima, P. Gomez-Sal, A. Martin, Organometallics 2004, 23,
5096–5099.
[4] a) C. R. Graves, B. L. Scott, D. E. Morris, J. L. Kiplinger, J.
Am. Chem. Soc. 2007, 129, 11914–11915; b) C. R. Graves, P.
Yang, S. A. Kozimor, A. E. Vaughn, D. L. Clark, S. D. Conrad-
son, E. J. Schelter, B. L. Scott, J. D. Thompson, P. J. Hay, D. E.
Morris, J. L. Kiplinger, J. Am. Chem. Soc. 2008, 130, 5272–
5285; c) C. R. Graves, B. L. Scott, D. E. Morris, J. L. Kiplinger,
Organometallics 2008, 27, 3335–3337; d) C. R. Graves, E. J.
Schelter, T. Cantat, B. L. Scott, J. L. Kiplinger, Organometallics
2008, 27, 5371–5378; e) C. R. Graves, A. E. Vaughn, E. J.
Schelter, B. L. Scott, J. D. Thompson, D. E. Morris, J. L. Kip-
linger, Inorg. Chem. 2008, 47, 11879–11891.[4a,4e]
[5] Attempted oxidation of (C5Me5)2U(=N-2,6-iPr2-C6H3)(THF)
(3) using in situ-formed CuMe from the reaction of CuI and
MgMe2 resulted in a mixture of both (C5Me5)2U(=N-2,6-iPr2-
C6H3)(Me) (4) and (C5Me5)2U(=N-2,6-iPr2-C6H3)(I) by 1H
NMR spectroscopy.[4a,4e]
[6] B. H. Lipshutz, in Organometallics in Synthesis, 2nd ed. (Ed.:
M. Schlosser), Wiley-VCH, Weinheim, 2002.
[7] Energetic Materials: Physics and Chemistry of Inorganic Azides,
Vol. 1 (Eds.: H. D. Fair, R. F. Walker), Plenum Press, New
York, 1977.
[8] Related silver azido complexes are also highly toxic and un-
stable/explosive; see ref.[7] and B. P. Aduev, E. D. Aluker, V. G.
Kriger, Y. A. Zakharov, Solid State Ionics 1997, 101–103, 33–
36.
[9] a) Au-alkyl: Y. Usui, J. Noma, M. Hirano, S. Komiya, Inorg.
Chim. Acta 2000, 309, 151–154; b) Au-alkenyl: D. V. Partyka,
J. B. Updegraff, M. Zeller, A. D. Hunter, T. G. Gray, Organo-
metallics 2007, 26, 183–186; c) Au-aryl: D. V. Partyka, M.
Zeller, A. D. Hunter, T. G. Gray, Angew. Chem. 2006, 118,
8368–8371; Angew. Chem. Int. Ed. 2006, 45, 8188–8191; d) Au-
alkynyl: W. Lu, N. Zhu, C.-M. Che, J. Am. Chem. Soc. 2003,
125, 16081–16088; e) Au-azide: W. Beck, T. M. Klapötke, P.
Klüfers, G. Kramer, C. M. Rienacker, Z. Anorg. Allg. Chem.
2001, 627, 1669–1674.
[10] a) W. J. Evans, K. A. Miller, J. W. Ziller, A. G. DiPasquale, K. J.
Heroux, A. L. Rheingold, Organometallics 2007, 26, 4287–
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Synthesis of (C5Me5)2U(O-2,6-iPr2-C6H3)(F) (5) by Oxidation of
(C5Me5)2U(O-2,6-iPr2-C6H3)(THF) (1) with CuF2: A 125-mL side-
arm flask equipped with a magnetic stir bar was charged with
(C5Me5)2U(O-2,6-iPr2-C6H3)(THF) (1) (0.75 g, 0.99 mmol) and
toluene (35 mL). To the dark green solution solid CuF2 (0.20 g,
1.98 mmol) was added resulting in an immediate color change to
dark red. After stirring at room temperature for 12 h, the reaction
mixture was filtered through a Celite-padded coarse porosity frit,
and the Celite pad was washed with toluene (10 mL) until the
washings went colorless. The filtrate was collected and the volatiles
were removed under reduced pressure to give a red oily residue.
This material was dissolved in hexane (35 mL) and the resulting
solution was filtered through a Celite-padded coarse porosity frit,
and the Celite pad was washed with hexane (10 mL) until the wash-
ings went colorless. The filtrate was collected and the volatiles re-
moved under reduced pressure to give a tarry red solid. Trituration
with TMS2O (10 mL) and drying gave (C5Me5)2U(O-2,6-iPr2-
C6H3)(F) (5) as
a dark red microcrystalline solid (0.65 g,
0.92 mmol, 93%). X-ray quality crystals of 5 were obtained from
1
either saturated TMS2O or hexane solutions at –35 °C. H NMR
(300 MHz, [D6]benzene, 25°): δ = –45.47 (br, 1 H, CHMe2), –11.50
(s, 6 H, CHMe2), –11.36 (br, 1 H, CHMe2), –1.73 (s, 6 H, CHMe2),
3.18 (s, 30 H, C5Me5), 4.14 (d, J = 8 Hz, 1 H, m-Ar-H), 6.31 (t, J
= 8 Hz, 1 H, p-Ar-H), 6.77 (d, J = 8 Hz, 1 H, m-Ar-H) ppm. MS
(EI, 70 eV): m/z 704 [M+]. C32H47FOU (704.74): calcd. C 54.54, H
6.72; found C 54.47, H 6.95.
Supporting Information (see also the footnote on the first page of
this article): Full details regarding the synthesis and characteriza-
tion of complexes 2 and 8, as well as the results from NMR-tube
experiments described herein.
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Eur. J. Inorg. Chem. 2009, 1451–1455