Syntheses of the antimonides R2Sb- (R = Ph, Mes, tBu, tBu2Sb) and Sb73- by reactions of organoantimony hydrides or cyclo-(tBuSb)4 with Li, Na, K, or BuLi

Article abstract of DOI:10.1002/zaac.200400497

Reactions of R₂SbH with BuLi at -70°C in tetrahydrofuran (thf) lead to [R₂SbLi(thf)₃] [R = Ph (1) or R = Mes (2)]. The antimonides [tBu₂SbK(pmdeta)] (3) (pmdeta = pentamethyldiethylenetriamine), [Li(tmeda)₂

Full text of DOI:10.1002/zaac.200400497

Syntheses of the Antimonides R2Sb؊ (R ؍ Ph, Mes, tBu, tBu2Sb) and Sb73؊ by
Reactions of Organoantimony Hydrides or cyclo-(tBuSb)4 with Li, Na, K, or BuLi
H. J. Breunig*, M. E. Ghesner, and E. Lork
Bremen, Institut für Anorganische und Physikalische Chemie der Universität
Received November 18th, 2004.
Dedicated to Professor Gerd-Volker Röschenthaler on the Occasion of his 60th Birthday
Abstract. Reactions of R2SbH with BuLi at Ϫ70 °C in tetrahydro-
furan (thf) lead to [R2SbLi(thf)3] [R ϭ Ph (1) or R ϭ Mes (2)].
The antimonides [tBu2SbK(pmdeta)] (3) (pmdeta ϭ pentamethyl-
diethylenetriamine), [Li(tmeda)2][tBu4Sb3]·benzene (4) (tmeda ϭ
tetramethylethylenediamine), and [tBu4Sb3Na(tmeda,thf)] (5) result
from the reduction of cyclo-(tBuSb)4 by Li, Na, or K with pmdeta
or tmeda in thf. The primary stibanes RSbH2 [R ϭ Mes (6), 2-
(Me2NCH2)C6H2 (7)] are synthesized by reactions of RSbCl2 with
LiAlH4. PhSbH2 reacts with BuLi, and tmeda in toluene to give
[Sb7Li3(tmeda)3]·toluene (8). [Sb7Na3(pmdeta)3]·toluene (9) is ob-
tained from PhSbH2, Na in liqu. NH3, pmdeta and toluene. Crystal
structures are reported for 1Ϫ5 and 9.
Keywords: Antimony; Alkali metals; Hydrides
Introduction
thium reagents [15]. PhSbNa2 and (PhSb)2Na2 are produced
by reactions of PhSbH2 or (PhSb)6·C6H6 and sodium in
liquid ammonia [15, 16].
Alkalimetal diorgano antimonides, R2SbM (R ϭ alkyl,
aryl) are well known reagents which are prepared by metal-
ation of secondary stibanes, R2SbH with organo lithium
compounds or by reactions of tertiary stibanes or distib-
anes with alkali metals [1Ϫ3]. Antimony mono anions re-
sult also from reactions of cyclo-(tBuSb)4 with alkali metals.
Antimonides are often used in situ for further reactions,
however with auxiliary ligands also crystals are obtained.
Crystal structures were determined for salt like compounds
with separated antimonide anions, eg [Li(12-crown-
4)2][Ph2Sb]·1/3thf [4], [Li(12-crown-4)2][Ph4Sb3]·thf [4],
[K(pmdedta)2][tBu4Sb3] [5], and for complexes with coordi-
nation of antimonido ligands on the alkali metal centers,
[(Me3Si)2SbLi(dme)] (dme ϭ 1,2-dimethoxyethane) [6],
In the course of investigations of organometallic com-
pounds with Sb-alkali metal bonds [7Ϫ8] we studied reac-
tions of organoantimony hydrides and cyclostibines with
3Ϫ
Li, Na, K or BuLi leading to derivatives of Sb7 and or-
ganoantimony mono anions.
Results and Discussion
Solutions of Ph2SbLi or Mes2SbLi were prepared by metal-
ation of Ph2SbH or Mes2SbH with nBuLi in thf [4, 17, 18].
Cooling concentrated solutions gave red, air sensitive crys-
tals of [Ph2SbLi(thf)3] (1), or [Mes2SbLi(thf)3] (2). The no-
vel complexes are stable only in an inert atmosphere at low
temperatures. They decompose above 29 °C (1) or 36 °C (2)
with formation of black solids. The crystal structures of 1
and 2 consist of discrete R2SbLi(thf)3 molecules with coor-
dination of the antimony atoms on the lithium centers (Fig-
ures 1 and 2). In crystals of 2 there are two independent
molecules with almost similar bond lengths and angles.
The antimony atoms have a trigonal pyramidal geometry
(Σ(bond angles at Sb) ഠ 289° in 1 and 307° in 2), while the
lithium atoms are in tetrahedral environments. The Sb-Li
[RRЈSbLi(thf)2], RRЈSbNa(tmeda) [R
RЈ ϭ 2-(Me2NCH2)C6H4] [7], [(tBu2Sb)2SbM(pmdeta)]
(M Na, K) [8], [(tBu2Sb)(tBu)SbK(pmdeta)] [8],
ϭ (Me3Si)2CH,
ϭ
[(CyP)4SbNa(tmeda)(Me2NH)] (Cy ϭ C6H11) [9] . The lat-
ter complex and [{Sb(PCy)3}2Li6(Me2NH)6] decompose to
the
Zintl
compounds
[Sb7Na3(tmeda)3(thf)3],
[Sb7Li3(HNMe2)6] and [Sb7Li3(tmeda)3]·toluene [9Ϫ11].
[Sb7Na3(2,2,2-crypt))3] and [Sb7K3(2,2,2-crypt))3·2en] are
formed from alkalimetal/antimony alloys [12, 13].
Very little is known of alkali metal monoorgano anti-
monides or related species [1Ϫ3]. Metalation of the stable
stibane RSbH2 (R ϭ [2,4,6-iPr3C6H2]2C6H3) with BuLi-
gives RSb(Li)H [14]. Complex mixtures of lithium phenyl-
antimonides were obtained from PhSbH2 and organoli-
˚
˚
bond lengths [2.881(4) A in 1 and 2.945(13), 2.893(15) A in
2] correspond well to values for the Sb-Li bond lengths
found
in
[(Me3Si)2SbLi(dme)],
2.933(4)
[6],
[Sb7Li3(HNMe2)6], 2.90(2) Ϫ 2.90(2) [10], and [Sb7Li3-
˚
(tmeda)3] · toluene, 2.86(2) Ϫ 2.90(2) A [10]. The geometries
of the diarylantimony groups in 1 and 2 and in [Li(12-
crown-4)2][Ph2Sb]·1/3thf [4] and [Mes2SbCuPMe3]2 [17] are
also similar.
[(tBu2Sb)K(pmdeta)] (3) was obtained by reacting cyclo-
(tBuSb)4 with pieces of potassium in refluxing thf for 2 h
45Ј, addition of pmdeta, and removal of the solvent.
* Prof. H. J. Breunig
Institut für Anorganische und Physikalische Chemie,
Universität Bremen,
28334 Bremen, Germany
Fax: ϩ 49/(0)421/2184042
E-mail: breunig@chemie.uni-bremen.de
Z. Anorg. Allg. Chem. 2005, 631, 851Ϫ856
DOI: 10.1002/zaac.200400497
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
851

H. J. Breunig, M. E. Ghesner, E. Lork
1
[8]. The H-NMR signal of (tBu2Sb)K in C6D6 appears at
δ ϭ 1.58.
3 is a red-brown solid, which is air and moisture sensitive,
but stable in an inert atmosphere. Crystals were grown by
cooling thf solutions at Ϫ28 °C. The structure of 3 (Figure
3) was determined by single crystal X-ray structure analysis.
The structure consists of polymers where tBu2Sb groups
and pmdeta-K units are in bridging positions between each
other and (Sb-K)x zig-zag-chains result. The coordination
around the Sb atom is distorted tetrahedral. The Sb-K
˚
bond lengths are 3.686(2) and 3.705(2) A. These values lie
in the range of the Sb-K bond lenghts found in
[(tBu2Sb)2SbK(pmdeta)],
3.833(6),
3.997(6)
and
˚
[tBu3Sb2K(pmdeta)] 3.5655(9) A [8]. The reduction of
cyclo-(tBuSb)4 with formation of [(tBu2Sb)2Sb]Ϫ is also
achieved by lithium or sodium in tetrahydrofuran. The re-
action time is however much longer for Li (3 d) than for K
(2 h) or Na (4 h). Crystals of [Li(tmeda)2][(tBu4Sb3)] · ben-
zene (4) and [(tBu4Sb3)Na(tmeda)(thf)] (5) are obtained
after addition of tmeda and cooling. The structures of 4
and 5 are shown in the Figures 4 and 5.
Figure 1 Structure of 1 in the crystal; the ellipsoids represent 40 %
˚
probability; selected bond lengths/A and angles/°:
Sb(1)-Li(1) 2.881(4); Sb(1)-C(1) 2.156(2); Sb(1)-C(7) 2.160(2); O(1)-Li(1)
1.953(4); O(2)-Li(1) 1.915(4); O(3)-Li(1) 1.936(4); C(1)-Sb(1)-C(7) 100.58(8);
C(7)-Sb(1)-Li(1) 96.96(9); C(1)-Sb(1)-Li(1) 91.77(9); Sb(1)-Li(1)-O(1)
115.24(16); Sb(1)-Li(1)-O(2) 114.68(17); Sb(1)-Li(1)-O(3) 114.20(17); O(1)-
Li(1)-O(2) 103.7(2); O(2)-Li(1)-O(3) 105.33(19); O(1)-Li(1)-O(3) 102.3(2);
C(7)-Sb(1)-Li(1)-O(3) 13.42(19); C(7)-Sb(1)-Li(1)-O(2) -108.28(18); C(7)-
Sb(1)-Li(1)-O(1) 131.43(18); C(1)-Sb(1)-Li(1)-O(1) 30.54(18); C(1)-Sb(1)-
Li(1)-O(2) 150.83(17); C(1)-Sb(1)-Li(1)-O(3)-87.47(18).
Crystals of 4 consist of two pairs of well separated
Ϫ
[Li(tmeda)2]ϩ and tBu4Sb3 ions and non coordinating
benzene molecules. The coordination sphere of the Liϩ ions
is fully occupied by the tmeda ligands. The structure of 5
contains discrete molecular complexes where the trianti-
monide ligands are coordinated to the sodium atoms
through both terminal antimony atoms. The Sb3Na hetero-
cycle in 5 is almost planar; the Na-Sb-Sb/Sb-Sb-Sb dihedral
angle is 175.5°. The bond lengths and angles [4, Sb-Sb
˚
2.768(1)Ϫ2.771(1) A; Sb3 89.37(1)°; 5, Sb-Na 3.241(3),
˚
˚
3.429(3) A; Sb-Sb 2.763(1), 2.754(1) A, Sb3 88.33(3)] are
similar with the corresponding values found in
˚
[K(pmdeta)2][(tBu2Sb)2Sb] [Sb-Sb 2.7643(9), 2.7669(7) A,
Sb3 86.23(3)°] [5] and [(tBu2Sb)2SbNa(pmdeta)] [Sb-Na
˚
3.304(2), 3.225 (2); Sb-Sb 2.720(8) Ϫ 2.776(2) A; Sb3
89.80(7), 91.4(2)°] [8].
The primary stibanes RSbH2 [R ϭ Ph, Mes (6), 2-
(Me2NCH2)C6H2 (7)] were prepared by reaction of the cor-
responding dichlorides with LiAlH4 in Et2O. 6 and 7 are
light and air sensitive colourless liquids, which are unstable
at room temperature but stable at Ϫ30 °C in an inert atmos-
Figure 2 Structure of one of the independent molecules in the asym-
metric unit of 2 in the crystal; the ellipsoids represent 40 % probabi-
lity; selected bond lengths/A and angles/°:
Sb(1)-Li(1) 2.945(13); Sb(1)-C(1) 2.182(6); Sb(1)-C(10) 2.190(6); O(1)-Li(1)
1
phere in absence of light. They were characterized by H-
NMR [δ SbH 3.11 (6), 4.43 (7)], IR [ν SbH 1863 (6), 1806
(7) cmϪ1] and mass spectrometry. Preliminary data of a
crystal structure analysis of 6 were reported recently [19].
The reaction of a solution of PhSbH2 in thf with nBuLi
in hexane (molar ratio 1:2) and tmeda in toluene in the
temperature range Ϫ70 to 0 °C leads to the formation of
red solutions. Crystallisation at Ϫ28 °C gives red crystals
of [Sb7Li3(tmeda)3]·toluene (8) in approximately 60 % yield.
This reaction provides a novel low temperature access to
this Zintl compound. We have redetermined the structure
of 8 and found conformity with the published data [10]. The
mechanism of the formation of 8 is not known. Attempts to
stabilize intermediates of the metalation by the use of pri-
mary stibines [6, 7, (Me3Si)2CHSbH2] which provide better
˚
1.945(15)
; O(2)-Li(1) 1.933(15); O(3)-Li(1) 1.961(13); C(1)-Sb(1)-C(10)
103.9(2); C(1)-Sb(1)-Li(1) 92.1(3); C(10)-Sb(1)-Li(1) 110.7(3); Sb(1)-Li(1)-
O(1) 112.3(5); Sb(1)-Li(1)-O(2) 109.8(6); Sb(1)-Li(1)-O(3) 120.5(6); O(1)-
Li(1)-O(2) 98.7(7); O(2)-Li(1)-O(3) 103.5(6); O(1)-Li(1)-O(3) 109.4(7); C(1)-
Sb(1)-Li(1)-O(1) 33.5(7); C(1)-Sb(1)-Li(1)-O(2) 142.2(5); C(1)-Sb(1)-Li(1)-
O(3) -97.8(7); C(10)-Sb(1)-Li(1)-O(1) 139.2(6); C(10)-Sb(1)-Li(1)-O(2)
112.1(5); C(10)-Sb(1)-Li(1)-O(3) 7.9(8).
-
Ϫ
Shorter reaction times lead to derivatives of tBu4Sb3 and
Ϫ
tBu3Sb2 in the sequence of reactions described in Scheme
1
1. The progress of the reaction can be monitored by H-
NMR spectra of samples taken from the reaction mixture
852
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zaac.wiley-vch.de
Z. Anorg. Allg. Chem. 2005, 631, 851Ϫ856

Syntheses of Antimonides
Scheme 1
Figure 4 Structure of the [Li(tmeda)2] [tBu4Sb3] unit in crystals of
4; the ellipsoids represent 40 % probability; selected bond lengths/
A and angles/°:
Sb(1)-Sb(2) 2.7706(5); Sb(2)-Sb(3) 2.7678(5); Sb(1)-C(1) 2.237(4); Sb(1)-C(5)
2.235(4); Sb(3)-C(9) 2.228(4); Sb(3)-C(13) 2.237(4); Li(1)-N(1) 2.110(7);
Li(1)-N(2) 2.111(7); Li(1)-N(1)# 2.110(7); Li(1)-N(2)# 2.111(7); C(1)-Sb(1)-
Sb(2) 99.51(12); C(5)-Sb(1)-Sb(2) 102.45(11); C(1)-Sb(1)-C(5) 104.39(17);
C(9)-Sb(3)-Sb(2) 100.54(12); C(13)-Sb(3)-Sb(2) 102.79(12); C(9)-Sb(3)-C(13)
103.20(17); Sb(1)-Sb(2)-Sb(3) 89.369(11); N(1)-Li(1)-N(2) 88.45(17); N(1)-
Li(1)-N(1)# 118.9(6); N(1)-Li(1)-N(2)# 121.14(16); N(2)-Li(1)-N(2)#
122.4(6); N(2)-Li(1)-N(1)# 121.14(16); N(1)#-Li(1)-N(2)# 88.45(17).
˚
Figure 3 Part of the zig-zag-chain structure of 3 in the crystal; the
ellipsoids represent 40 % probability; selected bond lengths/A and
angles/°:
Sb(1)-K(1) 3.6859(16); Sb(1)-C(1) 2.248(7); Sb(1)-C(5) 2.228(7); Sb(1)-K(1)#
3.7046(15); N(1)-K(1) 2.876(6); N(2)-K(1) 2.931(5); N(3)-K(1) 2.955(6)‚
C(1)-Sb(1)-C(5) 103.6(3); C(5)-Sb(1)-K(1) 100.8(2); C(1)-Sb(1)-K(1)
110.14(19); C(5)-Sb(1)-K(1)# 100.8(2); C(1)-Sb(1)-K(1)# 105.70(19); K(1)#-
Sb(1)-K(1) 131.87(4).
˚
Conclusion
sterical protection were not successful, compound 8 being
the only isolated product [19]. Red crystals of
[Sb7Na3(pmdeta)3]·toluene (9) were obtained by reacting
PhSbH2 with sodium inliquid ammonia and pmdeta in
toluene. The structure of 9 was determined by single crystal
X-ray diffraction. The structure is shown in Figure 6.
Crystals of 9 contain discrete cage molecules in which
Sb73Ϫ ions are coordinated through the equatorial Sb atoms
to three pmdeta solvated Naϩ cations. The Sb-Na bond
The metalation of Ph2SbH or Mes2SbH with BuLi is a
straight forward process leading to crystalline samples of
diarylantimonides. By contrast metalations of RSbH2 (R ϭ
Ph, Mes, 2-(Me2NCH2)C6H2, (Me3Si)2CH) result in the mi-
gration of the organic groups, formation of Sb-Sb bonds,
and open a convenient low temperature route to Zintl com-
pounds containing the Sb73Ϫ ion. Further investigations are
necessary to gain insight into this multi step process. Much
more is known of the reactions of the cyclostibane cyclo-
(tBuSb)4 with alkali metals, where the fission of Sb-Sb
bonds is accompanied by alkyl group migration reactions
and the successive formation of tri-, bi- and mononuclear
antimonides is well documented. The crystallographic
characterization of dianionic organo antimonides remains
a challenge for future research. The organo mono antimon-
˚
lengths range from 3.217(5) to 3.273(4) A and the values
for the Sb-Sb bond lengths lie between 2.737(1) and
3Ϫ
˚
2.880(2) A. The other known complex of Sb7 with ion-
contacts between Na and Sb is [Sb7Na3(tmeda)3(thf)3]. In
the latter complex there is an asymmetrical coordination of
the Naϩ cations and two of them form weak interactions
with the apical Sb atom [9]. In 9 the arrangement of the
coordinating Sb atoms and the Naϩ ions is almost planar.
3Ϫ
ides and the trianionic Sb7 ions are good ligands for the
Z. Anorg. Allg. Chem. 2005, 631, 851Ϫ856
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© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
853

H. J. Breunig, M. E. Ghesner, E. Lork
with a Bruker DPX 200 spectrometer. The products 1Ϫ8 were
characterised by single crystal X-ray diffraction (1Ϫ5, 8), NMR,
IR, and mass spectrometry. The compounds were not chararacter-
ized by elemental analyses because they are too unstable. The crys-
tal structure measurement and refinement data for 1Ϫ5 and 9 are
given in Tables 1 and 2. The data were collected on a Siemens P4
four-circle or a Stoe IPDS diffractometer using graphite-monoch-
˚
romated Mo Kα radiation (λ ϭ 0.71073 A). For this purpose the
crystals were attached with Kel-F oil to a glass fibre and cooled in
a nitrogen stream to 173 K. The structures were solved by direct
methods. All non-hydrogen atoms were refined with anisotropic
thermal parameters. Structure solutions and refinements were car-
ried out using the software packages SHELX-93 or SHELX-97. 2
was refined as a racemic twin. Diagrams were created using the
Diamond program by Crystal Impact GbR. CCDC-246281 (1),
Ϫ246282 (2), Ϫ246285 (3), Ϫ246283 (4), Ϫ246284 (5) and Ϫ246280
(9) contain the supplementary crystallographic data for this paper.
These data can be obtained free of charge at www.ccdc.cam.ac.uk
[or from the Cambridge Crystallographic Data Centre, 12 Union
Road, Cambridge CB2 1EZ, UK (fax: ϩ44-1223-336-033; E-mail:
deposit@ccdc.cam.ac.uk].
Figure 5 Structure of the [(tBu4Sb3)Na(tmeda)(thf)] unit in crystals
of 5; the ellipsoids represent 40 % probability; selected bond
lengths/A and angles/°:
˚
Sb(1)-C(1) 2.232(7); Sb(1)-C(5) 2.238(7); Sb(1)-Sb(2) 2.7631(10); Sb(1)-Na(1)
3.429(3); Sb(3)-C(13)2.233(9); Sb(3)-C(9)2.235(8); Sb(2)-Sb(3)2.7542(8);
Sb(3)-Na(1)3.241(3); Na(1)-O(1) 2.275(6); Na(1)-N(1) 2.440(7); Na(1)-N(2)
2.502(7), C(1)-Sb(1)-C(5) 104.0(3); C(1)-Sb(1)-Sb(2) 102.5(2); C(5)-Sb(1)-
Sb(2) 100.7(2); C(1)-Sb(1)-Na(1) 127.6(2); C(5)-Sb(1)-Na(1) 118.6(2); Sb(2)-
Sb(1)-Na(1) 98.19(6); C(13)-Sb(3)-C(9) 104.6(4); C(13)-Sb(3)-Sb(2) 103.3(3);
C(9)-Sb(3)-Sb(2) 102.8(2); C(13)-Sb(3)-Na(1) 108.8(3); C(9)-Sb(3)-Na(1)
131.2(2); Sb(2)-Sb(3)-Na(1) 102.97(6); Sb(3)-Sb(2)-Sb(1) 88.33(3); O(1)-
Na(1)-N(1) 119.3(3); O(1)-Na(1)-N(2) 98.4(3); N(1)-Na(1)-N(2) 74.1(3).
Synthesis of [Ph2SbLi(thf)3] (1). A solution of Ph2SbH (3.00 g,
10.83 mmol) in thf (50 mL) was treated dropwise with n-BuLi
(6.76 mL, 1.6 M in hexane) at Ϫ70 °C. The red solution was
warmed to Ϫ10 °C with stirring. Reducing the volume of the solu-
tion in vacuo to 20 mL and cooling overnight at Ϫ28 °C gave 4.20 g
(78 %) red crystals of 1 (dec. 29 °C).
1H-NMR (200 MHz, C6D6): 1.39 (12H, thf), 3.56 (12H, thf), 7.03 Ϫ 7.09
(m, 6H, C6H5 Ϫ m ϩ p), 7.41 Ϫ 7.46 (m, 4H, C6H5Ϫo).
Synthesis of [Mes2SbLi(thf)3] (2). A solution of Mes2SbH (3.00 g,
8.31 mmol) in 50 mL thf was treated dropwise with n-BuLi
(5.19 mL, 1.6 M in hexane) at Ϫ70 °C. The red solution was
warmed to Ϫ10 °C with stirring. Reducing the volume of the solu-
tion in vacuo to 20 mL and cooling overnight at Ϫ28 °C gave 2.97 g
(61 %) orange crystals of 2 (dec. 36 °C).
1H-NMR (200 MHz, C6D6): 1.32 (12H, thf), 2.30 (s, 6H, CH3 Ϫ p), 2.73 (s,
12H, CH3 Ϫ o), 3.45 (12H, thf), 6.97 (s, 4H, C6H2 Ϫ m).
Synthesis of [(tBu2Sb)K(pmdeta)] (3). To a solution of cyclo-
(tBuSb)4 (1.00 g, 1.4 mmol) in 40 mL thf, 0.30 g (7.7 mmol) small
pieces of K were added and stirred with reflux for 21/2 h. To the
refluxing solution 0.88 mL (4.2 mmol) pmdeta were added, the red-
brown solution was cooled with stirring to r. t. and filtered through
a frit covered with kieselgur. Removal of the solvent under reduced
pressure gave 0.17 g (15 %) of 3 as a red-brown solid (dec.
113Ϫ117 °C). Suitable crystals for X-ray analysis were grown by
cooling thf solutions at Ϫ28 °C.
Figure 6 Structure of the [Sb7Na3(pmdeta)3] unit in the structure
of 9 in the crystal; one of the pmdeta ligands is omitted for clarity;
the ellipsoids represent 40 % probability; selected bond lengths/A:
Sb(1)-Sb(4) 2.7922(13); Sb(1)-Sb(2) 2.7926(12); Sb(1)-Sb(3) 2.7959(15);
Sb(2)-Sb(5) 2.7371(13); Sb(3)-Sb(7) 2.7512(15); Sb(4)-Sb(6) 2.7457(15);
Sb(5)-Sb(7) 2.8630(14); Sb(5)-Sb(6) 2.8682(14); Sb(6)-Sb(7) 2.8802(19);
Sb(2)-Na(2) 3.225(5); Sb(2)-Na(3) 3.240(5); Sb(3)-Na(2) 3.221(5); Sb(3)-
Na(1) 3.231(4); Sb(4)-Na(3) 3.217(5); Sb(4)-Na(1) 3.273(4).
˚
1H-NMR (200 MHz, C6D6): 1.58 (s, 18H, C(CH3)3), 2.08 (s, 12H, N(CH3)2),
2.12 (s, 3H, NCH3), 2.23Ϫ2.41 (m, 8H, CH2). 13C-NMR (50 MHz, C6D6):
29.59 (s, C(CH3)3), 31.93 (s, C(CH3)3), 42.96 (s, NCH3), 45.98 (s, N(CH3)2),
56.85 (s, CH2), 58.22 (s, CH2).
Synthesis of [(tBu4Sb3)][Li(tmeda)2]·benzene (4). To a solution of
cyclo-(tBuSb)4 (1.00 g, 1.40 mmol) in 40 mL thf 0.97 g
(138.6 mmol) Li wire (Φ ϭ 0.6 mm) were added and stirred with
reflux for 3 days. After addition of 0.61 mL (4.13 mmol) tmeda
with 0.1 mL benzene and further stirring for 1 h at room tempera-
ture, the reaction mixture was filtered through a frit covered with
kieselgur. Cooling at Ϫ28 °C gives 0.20 g (17 %) of 4 as red crystals
(67 Ϫ 71 °C dec.).
coordination on alkali metal ions. Alkalimetal antimonides
with separated ions result only when the coordination
sphere of the cations is saturated by efficient multidentate
auxiliary ligands.
Experimental Section
1H-NMR (200 MHz, C6D6): 1.83 (s, 36H, C(CH3)3), 2.08 (s, 24H, N(CH3)2),
2.20 (s, 8H, CH2). 13C-NMR (50 MHz, C6D6): 32.56 (s, C(CH3)3), 35.42 (s,
C(CH3)3), 48.31 (s, N(CH3)2), 59.27 (s, CH2).
General. Syntheses were carried out under argonusing dried sol-
vents freshly distilled under argon. NMR spectra were recorded
854
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
zaac.wiley-vch.de
Z. Anorg. Allg. Chem. 2005, 631, 851Ϫ856

Syntheses of Antimonides
Table 1 Data for the X-ray structure determinations of 1 Ϫ 3
1
2a)
3
formula
formula weight
colour
C24H34LiO3Sb
499.20
red
C30H46Li O3Sb
583.36
red
C17H41KN3Sb
448.38
red
temperature/K
crystal size /mm
crystal system
space group
173(2)
173(2)
173(2)
0.60 x 0.50 x 0.40
triclinic
0.50 x 0.40 x 0.20
monoclinic
P21
10.079(2)
18.368(3)
16.729(2)
0.60 x 0.30 x 0.10
monoclinic
P21/c
6.748(1)
17.901(4)
20.510(4)
¯
P1
˚
a /A
9.149(1)
9.395(1)
15.957(2)
95.38(1)
100.63(1)
113.73(1)
2
1.367
1.158
512
˚
b /A
˚
c /A
α /°
β /°
γ /°
Z
103.27(1)
94.24(3)
4
4
d
/g cmϪ3
1.285
0.941
1216
1.205
1.287
936
calc
μ /mmϪ1
F(000)
θ range /°
2.51- 27.50
Ϫ11 Յ h Յ 11,
Ϫ11 Յ k Յ 11,
Ϫ20 Յ l Յ 20
6635
5500 [R(int) ϭ 0.0185]
5500 / 0 / 264
DIFABS
0.0271
2.50 Ϫ 27.50
Ϫ1 Յ h Յ 13,
Ϫ1 Յ k Յ 23,
Ϫ21 Յ l Յ 21
8887
7491 [R(int) ϭ 0.0305]
7491 / 2 / 646
DIFABS
0.0377
3.02Ϫ27.50
Ϫ1 Յ hՅ 8,
Ϫ1 Յ kՅ 23,
Ϫ26 Յ lՅ 26
7626
5652 [R(int) ϭ 0.0386]
5652 / 0 / 213
DIFABS
0.0601
Index ranges
No. of measured data
No. of unique data [R(int)]
Data / restraints / parameters
Absorption correction
R1 [I>2σ(I)]
wR2 [I>2σ(I)]
R1 (all data)
0.0694
0.0298
0.0917
0.0447
0.1311
0.1239
wR2 (all data)
0.0710
1.054
0.517, Ϫ0.744
0.0965
1.028
1.183, Ϫ0.920
0.1576
1.010
0.787, Ϫ1.295
goodness-of-fit on F2
Ϫ3
˚
residual density /e.A
a) 2 was refined as a racemic twin.
Table 2 Data for the X-ray structure determinations of 4, 5, and 9
4
5
9
formula
formula mass
colour
C34H74LiN4Sb3
911.16
red
C33H68N2NaOSb3
897.13
red
C34H77N9Na3Sb7
1533.27
red
temperature / K
crystal size /mm
crystal system
space group
173(2)
173(2)
173(2)
0.70 x 0.40 x 0.10
monoclinic
P2/c
17.802(2)
17.084 (2)
14.622(2)
93.60(2)
0.60 x 0.30 x 0.25
monoclinic
P21/n
13.345(3)
19.079(4)
16.754(3)
96.28(3)
0.8 x 0.6 x 0.6
orthorhombic
P212121
14.762(7)
17.616(2)
21.908(3)
90
˚
a /A
˚
b /A
˚
c /A
β /°
Z
d
4
4
4
/g cmϪ3
1.364
1.837
1848
1.405
1.931
1808
1.788
3.321
2936
calc
μ /mmϪ1
F(000)
θ range /°
2.58Ϫ27.50
Ϫ23 Յ h Յ 23,
Ϫ22 Յ k Յ 1,
Ϫ18 Յ lՅ 18
12187
10095 [R(int) ϭ 0.0234]
10095 / 0 / 404
DIFABS
0.0386
2.13Ϫ25.00
Ϫ15 Յ h Յ 1,
Ϫ22 Յ k Յ 1,
Ϫ19 Յ lՅ 19
9149
7437 [R(int) ϭ 0.0375]
7437 / 1 / 370
DIFABS
0.0506
2.59Ϫ27.49
Ϫ18 Յ h Յ 1,
Ϫ22 Յ k Յ 1,
Ϫ28 Յ l Յ 1
8668
8249 [R(int) ϭ 0.0316]
8249 / 0 / 499
DIFABS
0.0457
index ranges
no. of measured data
no. of unique data [R(int)]
data / restraints / parameters
absorption correction
R1 [I>2σ(I)]
wR2 [I>2σ(I)]
R1 (all data)
0.0758
0.0659
0.0811
0.1135
0.0876
0.0828
wR2 (all data)
0.0855
1.004
0.785, Ϫ0.968
0.0981
0.998
0.463, Ϫ0.493
0.1061
1.036
0.622, Ϫ0.714
goodness-of-fit on F2
Ϫ3
˚
residual density /e.A
Z. Anorg. Allg. Chem. 2005, 631, 851Ϫ856
zaac.wiley-vch.de
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
855

H. J. Breunig, M. E. Ghesner, E. Lork
Synthesis of [(tBu4Sb3)Na(tmeda)(thf)]·toluene (5). 1.00 g (1.4
mmol) cyclo-(tBuSb)4 was reacted for 4 h with small pieces of Na
(0.4 g, 17.4 mmol) in 40 mL thf. Afterwards 0.30 mL (2.06 mmol)
tmeda were added and stirred for 1 h until r.t.. After filtration and
removal of the solvent under reduced pressure 0.82 g of red solid
(78Ϫ84 °C dec.) was obtained. After recrystallization from toluene
at Ϫ28 °C 0.60 g (54 %) of 5 formed as red crystals.
dition of 2.07 mL (9.94 mmol) pmdeta in 10 mL toluene mixture
was allowed to warm to room temperature and ammonia was eva-
porated. Cooling to Ϫ28 °C gave 1.14 g (56 %) of 9 as red crystals.
Acknowledgements. We thank L. Opris and P. Brackmann for help
with the X-ray crystal structure analyses and the Deutsche For-
schungsgemeinschaft for financial support.
1H-NMR (200 MHz, C6D6): 1.77 (s, 36H, C(CH3)3), 1.95 (s, 4H, CH2), 2.02
(s, 12H, NCH3). 13C-NMR (50 MHz, C6D6): 25.75 (s, thf), 30.42 (s,
C(CH3)3), 34.89 (s, C(CH3)3), 46.05 (s, N(CH3)2), 57.77 (s, CH2), 67.80 (s,
thf).
References
[1] M. Wieber, in Gmelin Handbook of Inorganic Chemistry, Sb
Organoantimony Compounds, part 2, (Ed.: H. Bitter), Springer
Berlin, 1981.
[2] K.-Y. Akiba, Y. Yamamoto, in The Chemistry of Organic Ar-
senic, Antimony and Bismuth Compounds, (Ed.: S. Patai),
Wiley, Chichester, 1994.
[3] W. I. Cross, S. M. Godfrey, C. A. McAuliffe, A. G. Mackie,
R. G. Pritchard, in Chemistry of Arsenic, Antimony and Bis-
muth, (Ed.: N. C. Norman), Blackie Academic and Pro-
fessional, London, 1998.
[4] R. A. Bartlett, H. V. R. Dias, H. Hope, B. D. Murray, M. M.
Olmstead, P. P. Power, J. Am. Chem. Soc. 1986, 108, 6921.
[5] H. Althaus, H. J. Breunig, J. Probst, R. Rösler, E. Lork, J.
Organomet. Chem. 1999, 585, 285.
[6] G. Becker, A. Münch, C. Witthauer, Z. Anorg. Allg. Chem.
1982, 492, 15.
[7] H. J. Breunig, I. Ghesner, M. E. Ghesner, E. Lork, Inorg.
Chem. 2003, 42, 1751.
[8] H. J. Breunig, M. E. Ghesner, E. Lork, J. Organomet. Chem.
2002, 660, 167.
[9] A. Bashall, M. A. Beswick, N. Choi, A. D. Hopkins, S. J.
Kidd, Y. G. Lawson, M. E. G. Mosquera, M. McPartlin, P. R.
Raithby, A. J. Wheatley, J. A. Wood, D. S. Wright, J. Chem.
Soc. Dalton Trans. 2000, 479.
Synthesis of MesSbH2 (6). A solution of [2,4,6-(CH3)3C6H2]SbCl2
(2.00 g, 6.43 mmol) in Et2O (30 mL) was added dropwise to a cold
(Ϫ80 °C) suspension of LiAlH4 (0.52 g, 13.89 mmol) in Et2O
(20 mL). The mixture was warmed to Ϫ10 °C and filtered through
a cooled (Ϫ10 °C) frit covered with kieselgur. Removal of the sol-
vent under reduced pressure at Ϫ10 °C gave 1.42 g (92 %) of [2,4,6-
(CH3)3C6H2]SbH2 as a white solid unstable at room temperature
(m.p. Ϫ18 °C; dec. 15-18 °C). Suitable crystals for XϪray diffrac-
tion studies were grown by cooling a Et2O solution of MesSbH2
at Ϫ28 °C.
1H-NMR (200 MHz, C6D6): 2.10 (s, 3H, CH3Ϫp), 2.23 (s, 6H, CH3Ϫo), 3.11
(s, 2H, SbH2), 6.75 (s, 2H, C6H2Ϫm). 13C-NMR (50 MHz, C6D6): 20.88 (s,
CH3Ϫp), 27.90 (s, CH3Ϫo), 128.07 (s, C6H2), 128.29 (s, C6H2), 137.84 (s,
C6H2), 144.11 (s, C6H2). IR (Et2O): ν(Sb-H) 1863 cmϪ1 br. MS (EI, 70 eV)
m/z (%): 242 (43) [Mϩ], 119 (100) [Mesϩ], 105 (86) [MesϩϪCH3], 91 (40)
[MesϩϪ2CH3] Mes ϭ 2,4,6-(CH3)3C6H2. HRMS (EI, 70 eV): 242.00528
(calcd 242.00555 amu, C9H13Sb121).
Synthesis of [2-(Me2NCH2)C6H4]SbH2 (7). A solution of 1.00 g
(3.05 mmol) of [2-(Me2NCH2)C6H4]SbCl2 in Et2O (30 mL) was ad-
ded dropwise to a cold (Ϫ80 °C) suspension of LiAlH4 (0.25 g,
6.57 mmol) in Et2O (20 mL). The mixture was warmed to Ϫ30 °C
and filtered through a cooled (Ϫ30 °C) D4 frit covered with kiesel-
gur. Removal of the solvent under reduced pressure gave 0.68 g
(87 %) of [2-(Me2NCH2)C6H4]SbH2 as a white powder, unstable at
room temperature (m.p. Ϫ23 °C; dec. 11-14 °C).
[10] M. A. Beswick, N. Choi, C. N. Harmer, A. D. Hopkins, M.
Mc Partlin, D. S. Wright, Science 1998, 1500.
1H-NMR (200 MHz, C6D6): 1.98 (s, 6H, N(CH3)2), 3.18 (s, 2H, CH2N), 4.43
3
[11] M. A. Beswick, N. Choi, A. D. Hopkins, M. McPartlin, M.
E. G. Mosquera, P. R. Raithby, A. Rothenberger, D. Stalke,
A. J. Wheatley, D. S. Wright, Chem. Commun. 1998, 2485.
[12] D. G. Adolphson, J. D. Corbett, D. J. Merryman, J. Am.
Chem. Soc. 1976, 98, 7234.
(s, 2H, SbH2), 6.86 (d, 1H, C6H4, JHH ϭ 7.2 Hz), 7.19 Ϫ 7.32 (m, 2H,
C6H4), 8.03 (d, 1H, C6H4, 3JHH ϭ 6.7 Hz). 13C-NMR (50 MHz, C6D6): 45.14
(s, N(CH3)2), 65.46 (s, CH2N), 124.27 (s, C6H4), 126.79 (s, C6H4), 128.30 (s,
C6H4), 138.56 (s, C6H4),145.25 (s, C6H4). IR (Et2O): ν(Sb-H) 1806 cmϪ1 br.
MS (EI, 70 eV) m/z (%): 255 (65) [RSbϩ], 179 (28) [Me2NCH2Sb]ϩ, 134 (40)
[Rϩ], 58 (100) [Me2NCH2ϩ] R ϭ Me2NCH2C6H4.
[13] S. C. Critchlow, J. D. Corbett, Inorg. Chem. 1984, 23, 770.
[14] B. Twamley, C.-S. Hwang, N. J. Hardman, P. P. Power, J. Or-
ganomet. Chem. 2000, 609, 152.
[15] K. Issleib, A. Balszuweit, Z. Anorg. Allg. Chem. 1975, 418,
158.
[16] K. Issleib, A. Balszuweit, Z. Anorg. Allg. Chem. 1976, 419, 87.
[17] A. Cowley, R. A. Jones, C. M. Nunn, D. L. Westmoreland,
Angew. Chem. 1989, 101, 1089; Angew. Chem. Int. Ed. Engl.
1989, 28, 1018.
[18] K. Issleib, B. Hamann, Z. Anorg. Allg. Chem. 1966, 343, 196.
[19] M. E. Ghesner, Dissertation, Univ. Bremen, 2004.
Synthesis of [Sb7Li3(tmeda)3]·toluene (8). A solution of 2.00 g
(9.95 mmol) PhSbH2 in 30 mL thfwas cooled to Ϫ70 °C and n-
BuLi (12.44 mL, 1.6 M in hexane) was added via syringe. The solu-
tion was allowed to warm to 0 °C with stirring. At this temperature
tmeda (2.96 mL) in 10 mL toluene was added drop wise and the
mixture was stirred for 1 h. Cooling to Ϫ28 °C afforded 1.21 g
(65 %) red crystals of 8.
Synthesis of [Sb7Na3(pmdeta)3]·toluene (9). A solution of 2.00 g
PhSbH2 in 30 mL thf was added to 0.22 g (9.56 mmol) Na in 20 mL
liquid NH3 and the colour of the solution became red. After ad-
856
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
zaac.wiley-vch.de
Z. Anorg. Allg. Chem. 2005, 631, 851Ϫ856