5202
Organometallics 1998, 17, 5202-5205
Notes
Str u ctu r a l Tr a n sfor m a tion s of a Ser ies of
Tellu r iu m -Ir on Ca r bon yla tes a n d th e Isola tion of th e
Cu bic Clu ster [Te4F e4(CO)10(d p p m )]
Kuo-Chih Huang,† Mei-Huey Shieh,† Ren-J ay J ang,† Shie-Ming Peng,‡
Gene-Hsiang Lee,§ and Minghuey Shieh*,†
Department of Chemistry, National Taiwan Normal University, Taipei 11718,
Taiwan, Republic of China, and Department of Chemistry and Instrumentation Center,
National Taiwan University, Taipei 10764, Taiwan, Republic of China
Received J une 22, 1998
Summary: The cluster growth from the small anionic
cluster [TeFe3(CO)9]2- to the double-cubic cluster [Te10Fe8-
(CO)20]2- was systematically established. Further treat-
ment of [Te10Fe8(CO)20]2- with [Cu2(dppm)2(MeCN)4]-
[BF4]2 led to the formation of the new dppm-bridged
cubic cluster [Te4Fe4(CO)10(dppm)].
ing and understanding the conversion of small clusters
to larger ones is of great interest. In this paper, we
demonstrate a facile stepwise cluster growth from
[TeFe3(CO)9]2- to [Te10Fe8(CO)20]2-. The reactions of
[Te10Fe8(CO)20]2- with electrophiles are described as
well, from which the cubic cluster [Te4Fe4(CO)10(dppm)]
is obtained and compared with the double-cubic cluster
[Te10Fe8(CO)20]2-
.
In tr od u ction
Tellurium-rich metal compounds have attracted ex-
tensive attention, since tellurides exhibit unusual struc-
tural and reactivity patterns and are potentially pre-
cursors for new solid-state materials.1,2 Recently, a
series of novel tellurium-iron carbonylates have been
synthesized and structurally characterized by several
different methodologies. These interesting anionic clus-
Exp er im en ta l Section
All reactions were performed under an atmosphere of pure
nitrogen by using standard Schlenk line techniques.8 Solvents
were purified, dried, and distilled under nitrogen prior to use.
K2TeO3‚H2O (Alfa), TeO2 (Strem), Fe(CO)5 (Aldrich), and bis-
(diphenylphosphino)methane (dppm; Acros) were used as
received. Infrared spectra were recorded on a J asco 700 IR
or a Perkin-Elmer Paragon 500 spectrometer using CaF2 liquid
cells. Mass spectra were obtained on a Finnigan TSQ700 mass
spectrometer. Elemental analyses were performed on a Per-
kin-Elmer 2400 analyzer at the NSC Regional Instrumental
Center at National Taiwan University. 1H NMR spectra were
ters include [TeFe3(CO)12]2- 3a
, , [Te4Fe5-
[TeFe3(CO)9]2- 3,4
(CO)14]2- 5,6 [Te6Fe8(CO)24]2-,5 and [Te10Fe8(CO)20]2- 6
,
.
Nevertheless, their structural relationships and trans-
formations have never been systematically studied. The
reaction sequences in which the small molecules trans-
form to larger clusters are of great importance to the
extended inorganic solids.7 As a consequence, develop-
taken on a Varian 200 (200 MHz) instrument. [TeFe3(CO)9]2- 3,4
,
Te2Fe3(CO)9,9 and [Cu2(dppm)2(MeCN)4][BF4]210 were prepared
by the published methods.
F or m a tion of [Et4N]2[Te4F e5(CO)14]. To a mixture of
0.239 g (0.296 mmol) of [Et4N]2[TeFe3(CO)9] and 0.100 g (0.148
mmol) of Te2Fe3(CO)9 was added 20 mL of THF. After being
stirred for 3 days at room temperature, the solution was
filtered and solvent was removed under vacuum. The residue
was washed with hexanes and ether and then extracted with
CH2Cl2 to give 0.110 g (0.076 mmol) of [Et4N]2[Te4Fe5(CO)14]
(26% based on [Et4N]2[TeFe3(CO)9]). IR (νCO, MeCN) for
* To whom correspondence should be addressed.
† Department of Chemistry, National Taiwan Normal University.
‡ Department of Chemistry, National Taiwan University.
§ Instrumentation Center, National Taiwan University.
(1) (a) Ansari, M. A.; Ibers, J . A. Coord. Chem. Rev. 1990, 100, 223.
(b) Roof, L. C.; Kolis, J . W. Chem. Rev. 1993, 93, 1037. (c) Kanatzidis,
M. G.; Huang, S.-P. Coord. Chem. Rev. 1994, 130, 509.
(2) (a) Bogan, L. E., J r.; Lesch, D. A.; Rauchfuss, T. B. J . Organomet.
Chem. 1983, 250, 429. (b) Mathur, P.; Thimmappa, B. H. S.; Rheingold,
A. L. Inorg. Chem. 1990, 29, 4658 and references therein. (c) Mathur,
P.; Reddy, V. D.; Das, K.; Sinha, U. C. J . Organomet. Chem. 1991,
409, 255 and references therein. (d) Roof, L. C.; Pennington, W. T.;
Kolis, J . W. J . Am. Chem. Soc. 1990, 112, 8172.
[Et4N]2[Te4Fe5(CO)14]: 2025 w, 2008 s, 1975 vs, 1940 m cm-1
.
F or m a tion of [Et4N]2[Te6F e8(CO)24]. To a mixture of
0.100 g (0.069 mmol) of [Et4N]2[Te4Fe5(CO)14] and 0.086 g
(0.127 mmol) of Te2Fe3(CO)9 was added 40 mL of CH2Cl2. The
solution turned reddish brown immediately and was filtered,
and solvent was removed under vacuum. The residue was
washed with hexanes and ether and then extracted with
CH2Cl2 to give 0.110 g (0.051 mmol) of [Et4N]2[Te6Fe8(CO)24]
(3) (a) Bachman, R. E.; Whitmire, K. H. Inorg. Chem. 1994, 33, 2527.
(b) Roof, L. C.; Smith, D. M.; Drake, G. W.; Pennington, W. T.; Kolis,
J . W. Inorg. Chem. 1995, 34, 337.
(4) Shieh, M.; Chen, P.-F.; Tsai, Y.-C.; Shieh, M.-H.; Peng, S.-M.;
Lee, G.-H. Inorg. Chem. 1995, 34, 2251.
(5) Shieh, M.; Chen, P.-F.; Peng, S.-M.; Lee, G.-H. Inorg. Chem.
1993, 32, 3389.
(6) Roof, L. C.; Pennington, W. T.; Kolis, J . W. Angew. Chem., Int.
Ed. Engl. 1992, 31, 913.
(7) (a) Steigerwald, M. L.; Siegrist, T.; Stuczynski, S. M. Inorg.
Chem. 1991, 30, 4940. (b) Steigerwald, M. L.; Siegrist, T.; Gyorgy, E.
M.; Hessen, B.; Kwon, Y.-U.; Tanzler, S. M. Inorg. Chem. 1994, 33,
3389.
(8) Shriver, D. F.; Drezdzon, M. A. The Manipulation of Air Sensitive
Compounds; Wiley: New York, 1986.
(9) Lesch, D. A.; Rauchfuss, T. B. Inorg. Chem. 1981, 20, 3583.
(10) D´ıez, J .; Gamasa, P.; Gimeno, J .; Tiripicchio, A.; Camellini, M.
T. J . Chem. Soc., Dalton Trans. 1987, 1275.
10.1021/om980516f CCC: $15.00 © 1998 American Chemical Society
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