Communications
in KBr pellets were recorded on a Bruker Scimifar FTS 2000
[9] Y. V. Mironov, V. E. Fedorov, C. C. McLauchlan, J. A. Ibers,
Inorg. Chem. 2000, 39, 1809 – 1811.
spectrometer in the range 4000–375 cmꢀ1. Electrospray mass-spec-
trometric measurements were performed in the positive-ion mode on
a Q-Tof Ultima Global mass spectrometer.
[10] The reaction of ReS2 with KCN has been studied in the
temperature range from 650 to 8008C by using different ReS2/
KCN ratios. We found that for mass ratios of ReS2/KCN from 1:2
to 1:20 the main product of the reaction was K8[Re12CS17(CN)6].
1: ReS2 (1 g, 0.004 mol)and KCN (2 g, 0.03 mol)were heated in
an evacuated quartz tube at 7508C for 48 h. After the reaction
mixture had cooled, single crystals suitable for X-ray analysis were
selected. The product was washed with dry methanol to remove
excess KCN. A suspension of unconverted ReS2 was removed by
decantation with methanol. Yield: 0.65 g (60%). IR (KBr): n˜ = 383
To understand the conditions that yield [Re12CS17(CN)6]8ꢀ
,
KCs3[Re6S8(CN)6] was used as the starting material. It was
found that [Re6S8(CN)6]4ꢀ transforms into [Re12CS17(CN)6]8ꢀ if
the temperature rises to between 700 and 8008C. Furthermore,
the reaction of [Re6S8Br2] with KCN at high temperature also
gave the [Re12CS17(CN)6]8ꢀ cluster , whereas below 6508C
(w), 403, 417 (sh), 619 (w), 641, 720 (w), 755 (w), 912 (w), 2114 cmꢀ1
.
2: As for 1, ReS2 (1 g, 0.004 mol)and KCN (2 g, 0.03 mol)were
[Re6S8(CN)6]4ꢀ
formed.
These
data
indicate
that
heated in an evacuated quartz tube at 7508C for 48 h. The reaction
mixture was then dissolved in water (50 ml)and filtered. The filtrate
was heated under reduced pressure until the volume was about 5 mL
and the resulting solution was allowed to cool. The hexagonal plate
crystals that formed were isolated by filtration and dried in air. Yield:
0.76 g (80%). UV/Vis: l(e) = 330 (9100), 360 (6500), 445 (2240 sh),
505 (1400), 605 (310 sh), 735 (175), 1150 nm ( ꢁ 10 Lmolꢀ1 cmꢀ1) . IR
[Re12CS17(CN)6]8ꢀ cluster is thermodynamically stable within
the 650 to 8008C range.
[11] X-ray structural analyses: Bruker SMART CCD diffractometer
with area detector, graphite monochromator, MoKa radiation
(l = 0.71073 ), SHELX-97 program[27] for structure solution
(direct methods)and refinement (full-matrix least-squares on
F2). 1: C7K8N6Re12S17 (Mr = 3260.35), crystal size 0.14 0.13
0.03 mm, monoclinic, space group P21/m, a = 9.1806(11), b =
29.210(2), c = 9.2006(8), b = 119.777(1)o, V= 2141.5(4) 3,
Z = 2, 1calcd = 5.056 gcmꢀ3, m = 35.381 mmꢀ1, 2.55 < q < 28.218,
T= 293(2)K, face-indexed absorption correction (transmission
coefficient: 0.0831, 0.4598). Reflections: 13011 collected, 4890
unique (Rint = 0.0512), 3756 observed (I > 2s(I)). There were 239
parameters refined with R = 0.0619 (I > 2s(I)), wR2 = 0.1693 (all
data), GOF = 1.107, residual electron density: + 4.889/
ꢀ4.827 eꢀ3. 2: C7H40K6N6O20Re12S17 (Mr = 3542.47), crystal
size 0.12 0.12 0.03 mm, hexagonal, space group P63/mmc, a =
(KBr): n˜ = 406, 639, 719 (w), 757 (w), 882, 2116 cmꢀ1
.
3: Compound 3 was obtained by precipitation: CsCl (1 g,
0.006 mol)was added to an aqueous solution of 2, obtained as
above, to give 3 in quantitative yield. Single crystals were grown by
diffusion of methanol into a dilute aqueous solution of 3. IR (KBr):
n˜ = 382 (w), 405, 643, 721 (w), 764 (w), 939, 2120 cmꢀ1
.
Received: June 2, 2005
Published online: October 5, 2005
Keywords: cluster compounds · cyanides · density functional
.
10.8843(8), c = 27.840(4), V= 2856.3(5) 3, Z = 2, 1calcd
=
calculations · electronic structure · rhenium
4.119 gcmꢀ3, m = 26.427 mmꢀ1, 2.16 < q < 28.248, T= 293(2)K,
face-indexed absorption correction (transmission coefficient:
0.1436, 0.5044). Reflections: 16972 collected, 1383 unique (Rint
=
[1] a)Y. V. Mironov, A. V. Virovets, V. E. Fedorov, N. V. Podber-
ezskaya, O. V. Shishkin, Y. T. Struchkov, Polyhedron 1995, 14,
3171 – 3173; b)A. Slougui, Y. V. Mironov, A. Perrin, V. E.
Fedorov, Croat. Chem. Acta 1995, 68, 885 – 890.
0.0384), 1236 observed (I > 2s(I)), 82 parameters refined with
R = 0.0263 (I > 2s(I)), wR2 = 0.0589 (all data), GOF = 1.107,
ꢀ3
residual
electron
density:
+ 1.643/ꢀ2.408 e
.
3:
C7Cs6N6Re12S17 (Mr = 3746.34), crystal size 0.09 0.09
[2] N. G. Naumov, A. V. Virovets, N. V. Podberezskaya, V. E.
Fedorov, J. Struct. Chem. (Engl. Transl.) 1997, 38, 857 – 862.
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Am. Chem. Soc. 1997, 119, 493 – 498.
¯
0.01 mm, hexagonal, space group P62m, a = 9.7270(15), c =
14.629(3), V= 1198.7(4) 3, Z = 1, 1calcd = 5.190 gcmꢀ3, m =
35.407 mmꢀ1
,
2.42 < q < 28.188, T= 293(2)K, face-indexed
absorption correction (transmission coefficient: 0.1428, 0.6760).
Reflections: 7284 collected, 1105 unique (Rint = 0.0672), 913
observed (I > 2s(I)), 59 parameters refined with R = 0.0340 (I >
2s(I)), wR2 = 0.0915 (all data), GOF = 1.046, residual electron
density: + 2.391/ꢀ1.234 eꢀ3. Further details on the crystal
structure investigation may be obtained from the Fachinforma-
tionszentrum Karlsruhe, 76344 Eggenstein-Leopoldshafen, Ger-
many (fax: (+ 49)7247-808-666; e-mail: crysdata@fiz-karlsruhe.
de), on quoting the depository numbers CSD-415476–415478.
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Metal Clusters in Chemistry, Vol. 3, (Eds.: P.
Braunstein, L. A. Oro, P. R. Raithby), Wiley-VCH, Weinheim,
1999, pp. 1591 – 1611.
[15] To determine isotropic chemical shifts of carbons the 13C magic-
angle spinning (MAS)NMR measurements were made by using
a
BRUKER Bio-Spin Avance 400 MHz solid-state NMR
spectrometer. The spinning rate was 20 kHz, the p/2 pulse
duration was 5 s, the relaxation delay was 10 s. About 200 free
induction decays were accumulated at room temperature. TMS
was used as a reference. The 15N NMR spectrum contained one
sharp signal at 311 ppm (relative to NH3), which corresponds to
coordinated cyano ligands. No signal attributable to an inter-
stitial nitrogen atom was found. The diamagnetic properties of
[8] H. Imoto, N. G. Naumov, A. V. Virovets, T. Saito, V. E. Fedorov,
J. Struct. Chem. (Engl. Transl.) 1998, 39, 720 – 727.
ꢀ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2005, 44, 6867 –6871