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New Tellurometalates of Gallium and Indium K[K([18]crown-6)]2[GaTe3] ╖ 2CH3CN and [(NEt4)5][In3Te7] ╖ 0.5 Et2O

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E.upcritmwttrl Procrilurc
All manipulations were ciirried out under an argon atmosphere using standard
vacuum-linc and Schlenk techniques. The solvents were freshly distilled under nitrogen from the appropriate drying reagents. Phosphonium and ammonium salts were
dried in vacuum :it I X0 'C. Other reactants were used as received from the suppliers.
1 7 ZrX, ( X = CI: 0.466 g. 2.0 mmol: X = Br: 0.822 g, 2.0 mmol) was reduced
with Bu ,SnH I1.OZ mL. 4.0 mmol) in benzene or toluene (20 mL) for 36 h. The
resulting rcd-brown precipitate (dark blue for X = Br) was washed with two portions of freshly distilled toluene or benzene (each 10 mL) to remove excess Bu,SnH.
Addition oI'R,A'X- in CH,CN or CH,CI, afforded 1 in about 30% yield. Approximately SO'!. of starting material was unredcted and isolated as [R,A],[ZrX,].
Addition of P R , to the red-brown precipitate yielded a purple solution of compound 6 and e purple precipitate. Compounds 2 were isolated in about 1 5 % yield
by dissolviiig thc purple precipitate in CH,CI, and layering with hexane. When
phosphenes with ii higher number of carbon atoms (i.e., PBu,, P(lBu),Ph) were
used. the only iwlable products from crystallization were compounds 3 in about
I S % qield. Compounds 2 were converted into compounds 4 by treating with
[R,A]'CI- in ober 90% yield. Compounds 2 were also converted gradually into
compounds 5 in McCN solution at room temperature over a period of 30 days in
about 50"4 yield. When compounds 2 were further reduced with Na/Hg in the
prescnce of PR, compounds 7 were formed in yields of about 20%.
' H NMR rneiasurements were made at 200 MHz on a Varian XL-200 spectrometer.
Hydridc signals were detected at 6 = 3.07 for [Zr,CI,,HJ- and a t 6 = - 5.19
for [Zr,CI,,H,]"
in CH ,CN. X-ray data were collected on an Enraf-Nonius CAD4 dii'fi-iictoineter o r Enrdf-Nonius FR590 area detector. Full reports on the structures will be published elsewhere at a later time.
~
~
Received: April 18. 1995 [Z7891IE]
German version: Angeu.. Cliem. 1995. 107. 2050-2052
Keywords: clusters . hydrides . structure elucidation . zirconium
compounds
[I] F. A Cotton P A. Kibala. W. J. Roth, J. Am. Clwm. So<. 1988, 110. 298.
121 See, for example, F. Rogel. J. D. Corbett. .I Am. Chetn. Soc. 1990, IfZ. 8198.
[3] F. A. Cottoii. X . Feng, M. Shang, W. A. Wojtczdk. Angew. Chem 1992. 104,
1 1 17: ,4ngpii. ( ' h e n . , lnf.Ed. Engl. 1992, 3 f . 1050.
[4] F .A Cotton. W. A. Wojtczak. lnorg Cltim. Ac,ra 1994. 223, 93.
[5] I+. A . Cottoii. J. Lu. M. Shang, W. A. WOJtczdk. .I A t n . Chem. Sol. 1994. 116,
4364.
[6] G. M. Sheldrick, A Fortran-77 program for the refinement ofcrystal structures
from diffraction data: University of Gottingen, Gottingen, Germany, 1993.
[7] A. Simon. F. Bottcher. J. K. Cockcroft, Angcw. Chem. 1991, 103, 7 9 ; Angew
('Itam.. lnr Ed. Lng 1991. 30. 101.
[ X I The senior author would like to acknowledge that Dr. Arndt Simon made him
a friendly wager at the time ref. [3] was submitted that hydrogen atoms would
eventually hc found in our Zr, clusters.
New Tellurometalates of Gallium and Indium:
K[K([lS]~rown-6)]~[GaTe~~
2 CH,CN and
[ (NEt,),)[In,Te,] 0.5 EtzO**
-
Chang-Woo Park, Robert J. Salm, and James A. Ibers*
The number of known tellurometalates has increased rapidly
in the past few years through the use of the traditional techniques of nonaqueous solution chemistry as well as the nontraditional techniques of cathodic dissolution of electrodes composed of metal telluride alloys,[' -61 solvent extraction of metal
telluride phases,".
and solventothermal sealed-tube reactions.['Am ong these nontraditional techniques, the first
two have been especially effective for the synthesis of main
(*] Prof. .I. A. Ibers, C.-W. Park. R. J. Salm
[**I
Department of Chemistry, Northwestern University
Evanston. IL 60208-3113 (USA)
Telefax: Int. code + (708)491-7713
ernail. ibersrir chem.nwu.edu
This work was supported by the U. S. National Science Foundation, Grant
C'HE92-2446Y.
Awgrw ('lic~n? fnr. E d Engl. 1995. 34. No. 17
:(~;
group tellurometalates. The cathodic dissolution technique is
based on the constant discharge of tellurometalate anions into
the cathodic cell from the metal telluride electrode by application of a steadily increasing potential at room temperature; once
sufficient concentration has been achieved, crystallization may
occur in that chamber. The solvent extraction technique involves the high-temperature fusion of an alkali metal with the
desired elements for the tellurometalate, followed by extraction
with polar solvents such as ethylmediamine.
We have developed another synthetic route tor the preparation of tellurometalates, namely a chemical reduction method in
which binary metal tellurides are reduced in liquid NH, by K in
the presence of an encapsulating ligand.["] Through the use of
a chemical reducing agent, such as K, the potential remains
constant and is lower than is usual for cathodic dissolution
experiments. Through the use of liquid NH, as the solvent, the
reductions occur at much lower temperatures than are commonly used in the solvent extraction method or in redox reactions
in organic solvents, for example in the preparation of
[Ba(en),],[As,Te,] in refluxing ethylenediamine (en) .[201 For
this chemical reduction method to work an alkali-metal sequestering agent is necessary, since encapsulation of the cation helps
to prevent tight-ion pairing that otherwise would cause reversion of the compounds formed to insoluble materials.[8.211 The
features of lower reduction potential and lower temperature in
this chemical reduction method may enable the preparation of
tellurometalates that are not accessible by other techniques. We
illustrate that here with the synthesis and structural characterization of two new tellurometalates 1 and 2.
K[K([18]crown-6)],[GaTe3]
. 2CH,CN
[(NEt,),][In,Te,]
1
. 0.5Et20 2
Compound 1 was obtained as yellow plates from the chemical
reduction of Ga,Te,. Its crystal structure includes two
[K([18]crown-6)]+ ions, one K + ion, and two CH,CN solvent
molecules per [GaTe,13- ion. The [GaTe,13- ion, which has a
crystallographically imposed mirror plane through atoms G a
and Te(l), consists of a trigonal planar arrangement of Te atoms
about a central G a atom (Fig. 1). The Ga-Te distances are
2.495(3) and 2.513(2) A, the Te-Ga-Te angles are 114.76(11) and
122.38(6)", and the G a atom lies 0.10 8, above the plane of the
three Te atoms. These small distortions from strict trigonal planar geometry may be a result of the differing environments of
the Te atoms. For example, the K + ion, K(4), IS 3.429(1) A from
Te(1) and 3.797(1)8, from Te(2). The Ga-Te distances in
[GaTe,13- are similar to those reported for [PPh,][GaTe,(en),]
(2.509(1) A),[61but are signifi-cantly shorter than those in the
intermetallic compounds GaTe (average, 2.665(2) A),1221
Gd,Te,
(2.641(1) A),[221 and
K,Ga,Te, (2.591 and
Te(2)
2.680 A).r231Among
the combinations of
Group 13 (M) and
Group 16 (Q) elements
there
are
number of isolated
[MQ3I3- ions found
Fig. I . Structure of the [GaTee,]'- ion in 1 . Therin compounds pre- mal ellipsoids are shown at 50% probability. Relepared by high-&vant distances [A] and angles ['I: Ga-Te(1)
perature
solid-state 2.513(2). Ga- Te(2) 2.495(3j: Te(l)-Ga-Te(2)
Y
methods (for
the [BSe,13 - ion in
VCH ~,rlu~sg~,..Pllschu~/
nihH, DdY4Si Weinlzeim, I Y Y 5
122.38(6); Te(1)-Ga-Te(1Aj 114.76(11). The anion
has a crystallographically imposed mirror plane
through atoms Ga and Te(1).
US70-0N33/Y5!3417-/X7YS 10 00+ ,2511)
1879
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2: N H , (ca. 60 mL) was condensed into a flask that contained [2.2.2]cryptand
TI,BSe,[241), but the [GaTe,13- ion appears to be the first to be
(753 ing. 2 mmol) and K (80 ing, 2.0 mmol) at liquid N i temperature and the resulprepared at low temperatures by a solution method.
tant blue solution was stirred for 30 min at -78 ‘C. In2Te, powder (613 mg.
Compound 2 was obtained as orange needles from the chem1.0 mmol) was then added to the flask and the resultant mixture was stirred for 2
ical reduction of In,Te,. The [In,Te,15- ion, which has no
days to provide a red-brown solution. The NH, was allowed t o evaporate at room
temperature and CH,CN (IS mL) was added to the residual material. The resultant
known analogues, consists of an [In3Te4]’ cuboidal framework
solution was then filtered and NEt,Br (473 mg, 2.5 mmol) in CH,CN (15 mL) was
(where one corner is missadded to the filtrate. Et,O (90 mL) was layered on top of the solution to yield orange
ing) with one Te2- ligand
needles of 2 (180 mg. yield 22% based on Te).
on each of the three In3+
X-ray structurnl analysis: C,,H,,,,In,N,O, ,Te,. 0.58 x 0.12 xO.049 mm; monocenters (Fig. 2). This
clinic, P2,!rr. (I =12.419(6), h = 23.005(9). c = 24.171(10).&. /j =104.210(14)’.
I;= 6694(5)w3. T = 1 1 3 K : Z - 4 . pc4,c
=1.911 gcm-’. Picker diffractometer;
structure may be de20,,,,, = 49.5 ; Mo,,: i ( K z , ) = 0.7093 A; &20 mode: 13584 reflections measured.
scribed as three edge11544 independent reflections of which 11540 were included in the refinement: data
sharing “InTe,” tetrahecorrected for Lorenlz-polarization effects and for absorption (analytical method),
dra; each tetrahedron
p = 40.4 c1n-I. min.;max. trans. = 0.604;0.779; solution by direct methods [28],
refinement on F’ by fullmatrix least-squares [2Y], 244 parameters, 21 restraints.
shares an edge with each
anisotropic refinement of In and Te atoms. isotropic refinement of other non-hydroof the other two tetrahegen atoms; R , = 0.083. II’R, = 0.180. residual electron density = 2.27 e k ’ . Of the
dra. The In-Te,,,,i,,l
disfive independent NEt: ions only N(I)Et: is well defined; for this cation hydrogen
tances range from 2.685(2)
Fig. 2. Structure of the [Ln,Te,]’- ion in 2.
atoms were included at calculated positions. The N atoms and the four 1-C atoms
of the other four cations were modeled as rigid tetrahedra with N - - C bond lengths
Thermal ellipsoids are shown at 50% probto 2.692(2) A; the In-(p2ability. Relevant distances [A]and angles
of 1.50 A and C-N-C angles of 109.45”: [I-C atoms. when located. were restrained
Te) distances range from
[ 1: In(l)-Te(l) 2.802(2). In(1j-Te(3)
so that a C - / K bond lengths were 1.50(3) A.The number of/(-C atoms found for
2.802(2) to 2.824(2) A;
2.820(2). In(l)-Te(6) 2.691(2). In(l)-Te(7)
the N(n)Etf ions are- n = 2, four. but two dimrdered over two sites: n = 3. four:
the In-(kiL,-Te) distances
2.883(2). In(Z)-Te(l) 2.812(2). In(2)-Te(2)
n = 4. none: n = 5 , three. Some ofthe resultant displacement parameters are unrea2.824(2). In(2)- Te(4j 2.692(2), ln(2)-Te(7)
sonably large. probably because the model ofisotropically Vibrating rigid groups is
range from 2.881(2) to
inadequate. An Et,O solvent of crystallization is disordered about the origin. Fur2.907(2), In(3)-Te(2) 2.809(2), In(3) Te(3)
2.907(2) A. All of the
2.816(2). In(3)-Te(5) 2.685(2). In(3)-Te(7)
ther details of the crystal structiire investigations may he obtained from thc Director
“InTe,”
tetrahedra
are
2.897(2); Te(h)-In(l)-Te(l) 117.98(6), Te(6)of the Cambridge Crystallographic Data Center. 12 Union Road. GB-Cambridge
distorted and have Te-InCB21EZ (UK), on quoting the full journal citation.
In(1 )-Te(3) 120.56(7). Te(l)-In( 1 )-Te(3)
107.72(6). Te(h)-ln( 1)-Te(7) 114.09(6),
Te angles between 94.16(5)
Te(1)-In(l)-Te(7) 96.30(6), Te(3)-ln(1)-Te(7)
Received: March 29, 19Y5 [Z783Y IE]
and
120.56(7)’. This
German version: A i i g w . Chcm. 1995. 107. 2044- 2045
95.36(5). Te(4)-ln(2)-Te(l)118.30(7), Te(4)lengthening of the In-Te
ln(2)-Te(2) I16.65(6). Te(l)-In(2)-Te(2)
bonds with increasing co112.73(6). Te(4)-In(l)-Te(7) 114.83(6).
Keywords: gallium compounds . indium compounds . metalates .
Te(l)-In(2)-Te(7) 95.51(6). Te(Z)-In(2)-Te(7)
ordination number of the
tellurium compounds . Ziiitl phases
94.16( 5 ) . Te(5)-ln(3)-Te(2) 116.88(7), Te(5)Te atom is also seen in reIn(3)-Tc(3) 117.15(7). Te(2)-In(3)-Te(3)
lated systems. For ex113 00(6). Te(S)-In(3)-Te(7) 115.73(7).
ample, the “TnTe,” tetraTe(?)-ln(3)-Te(7)94.70(5), Te(3)-In(3)-Te(7)
[I] C. J. Warren. V. M. Ho, R. C. Haushalter, A. B. Bocarsly. Arig~iv.Chmii. 1993.
9 S.OY(5)
hedral moiety is contained
105. 1684; A n g w . Cliwii. In/ Ed. Ens/. 1993. 32, 1646.
in Na51nTe4,[”] in which
[2] B. Eisenmann. Angeiv. Chcm. 1993, 105. 1764; Arigcw. C/ieni.. In/.Ed. Engl.
the In- Telermlndl
distances
1993. 32. 1693.
[3] C. J. Warren, D. M. Ho. A. B. Bocarsly. R. C. Haushalter. J. Am. Ckvri. Six.
range from 2.758(2) to 2.81 l(2) A and the Te-In-Te angles are all
1993, 115. 6416.
nearly tetrahedral. The In-(p2-Te) bond lengths in
[4] C. J. Warren. S. S. Dhingra. D. M. Ho, R. C. Haushalter. A. B. Bocarsly,
[NBu,],[III,T~,][~~~
and in Na51n2Te6~zsJ
range from 2.786(2) to
Irrorg. C/wii. 1994. 33. 2709.
2.814(2) 8, and from 2.818(5) to 2.836(5) A, respectively. The
[S] C. J. Warren. R C. Haushalter. A. B. Bocarsly. Chon. Murcr. 1994, 6 . 780.
“In,Te,” cubaiie core is found in [ C ~ ( C O ) , M O ] , I ~ , T ~ , ;in[ ~ ~ ~ [6] C. J. Warren. D. M. Ho. R. C. Haushalter. A. B. Bocarily. J. C/imr. SIX. Chcni.
C’orumun. 1994. 361.
this compound the In-(p3-Te) distances range from 2.839( 1) to
[7] R. C. Burns, J. D. Corbett. /uorp;. C%c.wt.1981. 20, 4433.
2.989(1) A.
[XI S. S. Dhingra. R. C. Haushalter. /no,::. Chent. 1994. 33, 2735.
Esperimental Procedure
Ga,Te, and In,Te, were prepared by the fusion of stoichiomrtric amounts of the
constituent elements under an inert atmosphere and were finely ground before use.
1 : NH, (ca. 60 mL) was condensed into a flask that contained [18]crown-6 (528 mg,
2.0 mmol) and K (80 mg, 2.0 mniol) at liquid N, temperature and the resultant blue
solution was stirred for 30 min at - 78 ‘C. Ga,Te, (522 mg. I mmol) was then added
to the flask and the resultant mixture was stirred for 2 days to provide a light brawn
solution. The NH, was allowed to evaporate at room temperature and CH,CN
(30 inL) was added to the residual material. The resultant solution was then filtered.
Et,O (80 mL) was layered on top ofthe filtrate to afford yellow plates of 1 (1 10 ing,
yield 10% based on Te) after 5 days.
X-ray structural analysis: C,,H,,GaK,NZO,,Te,;
crystal dimensions,
0 04 x 0.16 x 0.23 mm; monoclinic, C2;nr; u = 24.469(5), h = 14.073(3). L‘ =
12.875(3).&, /i=
97.47(3), I;= 4369(2)A3; T = 1 1 3 K ; Z = 4 : /I,.,. =
1.784 gem-’;
Eni-af-Nonius CAD4 diffractometer; 20,m,,,= 120.6 ; Cu,,;
j.(Kx,) = 1.540862
( t i - 2 0 scan mode: 11538 reflections measured. 3342 independent reflections all of which were included in the refinement: data corrected for
Lorentz-polarization effects and for absorption (analytical method). /I = 192 cm- I .
min.;max. trans. = 0.065/0.446; solution by direct methods [28]. refinement on F z
by full-matrix least-squares [29]. 228 parameters. anisotropic refinement of nonhydrogen atoms, H atoms placed in calculated positions before final cycle of relinement; one CH,CN solvent molecule is disordered: use was made of the SQUEEZE
subroutine [30] of the PLATON softMare package [31] to account for its electron
density: R , = 0.0X0; II R , = 0.177: residual electron density = 1.03 e k ’ .
A;
[Y] W. S . Sheldrick. H.-J. Hiusler. Z . Anorp;. M p ; . Chern. 1988. 557. 105.
[lo] W. S. Sheldrick. H.-J. Hiusler, 2.Anorg. A&. Cliern. 1988. 257, 98.
[I 11 W. S. Sheldrick, Z. Anor& AUK. Choir. 1988. 562. 23.
[I21 W. S. Sheldrick. J. Kaub. Z. Anorg. AI/g. Chem. 1986, 535. 179.
113) J.-H. Liao. M . G . Kanatzidis. Inorp;. Chmr. 1992, 31, 431.
[I41 H. M. Haendler. D. Mootz. A. Rabenau, G. Rosenstein. J. Solid State Chcm
1974. 10, 175.
[IS] W. Milius, Z. N u l o u f h r w / i . B 1989. 44. 990.
[I61 C . Stergiou. P. J. Rentreperis. Z.Krr.\ro//ogr. 1985, 172. 1 1 1
[I71 J.-H. Chou, M . G. Kanatzidis. Inorp;. Cltrm. 1994, 33. 1001.
[IS] W. Milius. A. Rabenau, Z. Nururforsd?. B 1988. 43. 243.
[I91 C.-W. Park. R. J. Salm. J. A. Ibers, r u n . J. (’hem. 1995, in press.
[20] 9. Eisenmann. R. Zngler, Z . Nrrturfor.;di. B 1987, 42. 1079.
[21] J. V. Corbett, Chem. Rpi.. 1985, 8.7, 383.
[22] F. Alapini. J. Flahaut. M. Guittard. S. Jaulmes. M. Julien-Pouzol. J. SolidState
Clwn. 1979. 28, 309.
[23] B. Eisenmann. A. Hofmann. L. K~Y.\/a//ugr.1991, 197. 145.
[24] B. Krcbs. W. Hamann. J. Lc.wConinio,i Mi,/rr/.s1988. 137. 143.
[2S] B. Eisenmann, A. Hofmann. R. Zagler. Z. Nutruforsd. B 1990. 45. 8.
[26] C . J. Warren. S. S. Dhingra. R. C. Haushalter. A. B. Bocarsly, J. Solid Stare
C / i ~ i i .1994, 112. 340.
[27] K. Merzweiler. F. Rudolph. L. Brands. Z. Nrrlur/orsi/i. B 1992, 47, 470.
[28] G . M. Sheldrick, in C,:1.s/m//~i~~rtrp/ri(.
Cbr~rpurinp;3. (Eds.: G. M. Sheldrick,
C . Kruger, R. Goddard). Oxford University. London. 1985. pp. 175 189.
[2Y] G. M. Sheldrick. J. Appl. Crj..stu//ogr. 1995. in press.
[30] P v a n der Sluis. A. L. Spek, A~.tirCrv.stu//ogr. Sacr. A . 1990. 46. lY4.
1311 A. I.. Spek, Arrrr C r i ~ s r o / / o , ~.SLW/.
r.
A 1990. 46. C34.
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