Gallium and indium arsanido metalates: Compounds derived from the zinc blende and wurtzite structure

Article abstract of DOI:10.1002/(SICI)1521-3749(199906)625:6<954::AID-ZAAC954>3.0.CO;2-B

The reaction of InCl₃ with LiAs^tBu₂ in THF at -78°C gives the indium arsenide Cl₂InAs^tBu₂ (1), which is dimer in solution and solid state. The corresponding reaction of InCl₃ with Li₂As^tBu leads to the metalate [Li(THF)₄]₂[(InCl)₄(InCl₂) ₂(As^tBu)₆] (2). The arsanido metalate [Li(THF)₄]₂[(GaCl₂)₆(As ^tBu)₄] · THF (3 · THF) could be obtained by treatment of GaCl₃ with Li₂As^tBu in the molar ratio 6:4. A comparable reaction with TlCl₃ and LiAsR₂ or LiPR₂, respectively, was not successful because of the oxidation potential of TlCl₃. The reaction mixture of TlCl₃ and LiPPh₂ for example gives TlCl and Ph₂P-PPh₂ (4) as redox products. The octaarsane [As(As^tBu)₃]₂ (5) can be obtained by the treatment of ^tBuAs(SiMe₃)₂ with TlCl₃ in THF. 1-5 were characterized by NMR, IR and MS techniques. The X-ray analyses of 2 and 3·THF show that 2 can be derived from the wurtzite structure while the zinc blende structure is the model for 3 with a adamantane-like dianion [(GaCl₂)₆(As^tBu)₄]^2-.

Full text of DOI:10.1002/(SICI)1521-3749(199906)625:6<954::AID-ZAAC954>3.0.CO;2-B

Gallium and Indium Arsanido Metalates:
Compounds Derived from the Zinc Blende and Wurtzite Structure
Anahita Dashti-Mommertz and Bernhard NeumuÈller*
Marburg, Fachbereich Chemie der UniversitaÈt
Received 19th January 1999.
Abstract. The reaction of InCl3 with LiAstBu2 in THF at
±78 °C gives the indium arsenide Cl2InAstBu2 (1), which is
dimer in solution and solid state. The corresponding reaction
of InCl3 with Li2AstBu leads to the metalate
[Li(THF)4]2[(InCl)4(InCl2)2(AstBu)6] (2). The arsanido me-
talate [Li(THF)4]2[(GaCl2)6(AstBu)4] ´ THF (3 ´ THF) could
be obtained by treatment of GaCl3 with Li2AstBu in the mo-
lar ratio 6 : 4. A comparable reaction with TlCl3 and LiAsR2
or LiPR2, respectively, was not successful because of the oxi-
dation potential of TlCl3. The reaction mixture of TlCl3 and
LiPPh2 for example gives TlCl and Ph2P±PPh2 (4) as redox
products. The octaarsane [As(AstBu)3]2 (5) can be obtained
by the treatment of BuAs(SiMe3)2 with TlCl3 in THF. 1±5
were characterized by NMR, IR and MS techniques. The X-
ray analyses of 2 and 3 ´ THF show that 2 can be derived
from the wurtzite structure while the zinc blende structure
t
is the model for
3 with a adamantane-like dianion
[(GaCl2)6(AstBu)4]2±.
Keywords: Gallium arsanide; Indium arsanides; Lithium-
organo arsanides; Crystal structures
Gallium- und Indium-Arsanidometallate:
Verbindungen abgeleitet von der Zinkblende- und der Wurtzit-Struktur
InhaltsuÈbersicht. Die Reaktion von InCl3 mit LiAstBu2 in
THF bei ±78 °C ergibt das Indiumarsanid Cl2InAstBu2 (1),
das als Dimer in LoÈsung und im FestkoÈrper vorliegt. Die
entsprechende Umsetzung von InCl3 mit Li2AstBu fuÈhrt
zum Metallat [Li(THF)4]2[(InCl)4(InCl2)2(AstBu)6] (2). Das
folg. Die Reaktionsmischung von TlCl3 und LiPPh2 z. B. er-
gibt TlCl und Ph2P±PPh2 (4) als Redoxprodukte. Das Ok-
taarsan [As(AstBu)3]2 (5) wird bei der Umsetzung von
tBuAs(SiMe3)2 mit TlCl3 in THF gebildet. 1±5 wurden durch
NMR-, IR- und MS-Techniken sowie Kristallstrukturanaly-
sen charakterisiert. Die Ergebnisse der RoÈntgenstrukturana-
lysen von 2 und 3 ´ THF zeigen, daû 2 von der Wurtzit-Struk-
tur abgeleitet werden kann, waÈhrend die Zinkblende-
Struktur als Modell fuÈr 3 mit einem Adamantan-aÈhnlichen
Dianion [(GaCl2)6(AstBu)4]2± dienen kann.
Arsanidometallat
[Li(THF)4]2[(GaCl2)6(AstBu)4] ´ THF
(3 ´ THF) kann bei der Behandlung von GaCl3 mit Li2AstBu
im molaren VerhaÈltnis 6 : 4 erhalten werden. Eine vergleich-
bare Reaktion zwischen TlCl3 und LiAsR2 oder LiPR2
fuÈhrte aufgrund des Redoxpotentials des TlCl3 nicht zum Er-
i
1
Introduction
[M = Al, Ga; E = P, As; R = SiiPr3, SiMe2(CMe2 Pr)]
[20]. A limiting factor in growing the size of such com-
plexes is the bulk of the substituent on the metal and
the pnicogen atom. For the build-up of a larger archi-
tecture, containing the group 13/group 15 element
Part of the recent efforts and developments in the orga-
nometal chemistry of group 13 metals is due to their
possible use as single-source precursors for optoelectron-
ical and semiconducting materials via MOCVD (metal-
organic chemical vapor deposition) and MOVPE (me-
talorganic vapor phase epitaxy) methods [1±3]. At the
same time the interest in new cyclic and cage com-
pounds containing the atom combination group 13/
group 15 starts to grow [4±17]. However, cages with
group 13/As are still rare. Examples are the complexes
[({(Me3Si)2CH}2Ga)3Ga2(AsPh2)(AsPh){(H)AsPh}] [18],
combination,
a
versatile substituent pattern on
the metal would be one or more halogen atoms.
Compounds of this type are known in gallium
chemistry, e.g. [Br2GaAs(CH2SiMe3)2]3 [21] and
[I2GaAs(SiMe3)2]2 [22]. Subject of this study are the
reactions of simple metal trihalides with mono- and
dilithiumorgano pnictides in order to form metal inor-
ganic ring and cage aggregates.
i
[Li(DME)3][Li(DME)(AlH2)3{AsSiMe2(CMe2 Pr)}3]
[19] [Li4(OEt2)8(AlH)4(AsSiiPr3)3] [20] and [HMER]6
2
Results and Discussion
* Priv.-Doz. Dr. Bernhard NeumuÈller
Fachbereich Chemie der UniversitaÈt
Hans-Meerwein-Strasse, D-35032 Marburg (Germany)
Fax: int-64 21-28 89 17
Our standard method to form M±E bonds (M =
Al±In, E = N, P, As, S, Se, Te) is the treatment of the
corresponding organometal halides R2MX and RMX2
E-mail: neumueller@ax1502.chemie.uni-marburg.de
954
Ó WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999
0044±2313/99/625954±960 $ 17.50+.50/0
Z. Anorg. Allg. Chem. 1999, 625, 954±960

Gallium and Indium Arsanido Metalates
with a suitable lithium reagent LiER' or LiER'2 [12,
13, 17, 23]. We intended to extend the metathesis pro-
cedure to the metal halides MX3 of group 13. Our at-
tempts to synthesize compounds such as X2MPR'2 by
this method was not successful up to now.
However, the reaction of InCl3 with the diorgano-
lithium arsanide LiAstBu2 in THF at ±78 °C directly
gives Cl2InAstBu2 in good yield [Eq. (1)].
and (PhCH2)2InPPh2 [17]. The resonances for the two
tBu groups and one of the THF signals give a broad
multiplet in the proton NMR spectrum of 2. However,
the 13C NMR signals of the differing t-butyl substitu-
ents are separated (31.2, 34.9 ppm and 50.0,
51.3 ppm).
1
One can expect only one H NMR signal for the
CH3-groups in the dianion of 3, which was detected at
1.92 ppm. The 31P NMR resonance for the wellknown
compound 4 was found at ±13.6 ppm [25, 26].
THF 78 C
InCl3 + LiAstBu2
Cl2InAstBu2 + LiCl
(1)
1
The two IR active In2As2 ring vibrations as well as
the asymmetric and the symmetric InCl2 vibrations
are responsible for two broad absorptions at 250 and
327 cm±1, respectively. The dianion in 2 causes a mInCl
band for the ClInAs3 moiety at 316 cm±1 and a mInCl2
band for the Cl2InAs2 moiety at 281 cm±1. The absorp-
tion at 209 cm±1 is due to the asymmetric cage vibra-
tion mIn6As6. The dianion in 3 possesses nearly Td-
symmetry and shows the band for the asymmetric
cage vibration mGa6As4 at 247 cm±1. masGaCl2 and
msGaCl2 were assigned to the signals at 331 and
296 cm±1, respectively.
Keeping the same molar ratio of 1 : 1 of the educts
InCl3 and Li2AstBu at similar conditions the hexanu-
clear complex 2 was obtained [Eq. (2)].
6 InCl3 + 6 Li2AstBu
1 Et2O 78 C
2 THF
[Li(THF)4]2[(InCl)4(InCl2)2(AstBu)6] + 10 LiCl
(2)
2
Although we performed the reaction of GaCl3 and
Li2AstBu also with a molar ratio of 1 : 1 only the com-
pound 3 could be isolated. A clear increase of the
yield was found after modifying the stoichiometry to
6 : 4 [Eq. (3)].
The heaviest mass particle was found for m/z = 300
[(ClInAs2)+] in the EI mass spectra of 1, 2 and 3
([Ga2As(C4H9)2]+), while in the spectrum of 4 the M+
peak could be detected at m/z = 370.
6 GaCl3 + 4 Li2AstBu
1 Et2O 78 C
2 THF toluene
[Li(THF)4]2[(GaCl2)6(AstBu)4] ´ THF + 6 LiCl
(3)
3 ´ THF
3
X-ray analyses of [1]2±4
The structure of [Cl2InAstBu2]2 ([1]2) consists of cen-
trosymmetric four-membered In2As2 rings with D2h
symmetry (Figure 1). The atoms In1, Cl1 and Cl2 lie
on a mirror plane while a twofold axis is running
through As1. The bond length In1±As1 of 265,2(1) pm
is short in comparison with other In2As2 compounds,
probably due to the two electronegative Cl ligands
[23]. Quite similar are the In±As distances in
[Ph2InAs(SiMe3)2]2 with 265,7(3)±267,9(2) pm [24]. It
is possible to obtain 1 also in a trimer modification by
crystallization. Although the crystals of [1]3 were of
no good quality we were able to solve the structure.
Here, the basic structural motif was a distorted boat
conformation. In general, the existence of two or
more oligomers of one derivative R2M-ER'2 is not
unusual [17].
The asterane-like centrosymmetric dianion
[(InCl)4(InCl)2(AstBu)6]2± contains two In±As six-
membered rings (Figure 2) in a distorted boat confor-
mation, which are connected by four In±As bonds to
form two additional In±As four-membered rings. The
In±As bonds involving In2 and As1 are significantly
shorter (259 pm; mean value) than the corresponding
values within the four-membered rings (267 pm). The
reason is probably the l2-bridging function of In2 and
As1 concerning other In and As atoms, respectively.
Typical distances in four-membered In±As he-
terocycles such as [(PhCH2)2InAstBu2]2 [23] or
The mixtures containing lithium arsanides or phospha-
nides and TlCl3 very often gave precipitation of ele-
mental thallium and LiCl. This was caused by the pri-
mary step, a reduction of TlCl3 to TlCl [Eq. (4)]. The
further reaction of TlCl with Li-reagents such as
LiPR'2 gave unstable TlI phosphanides which under-
goe disproportionation to TlIII species and Tl metal.
The pnictide compounds were oxidized under E±E
coupling in the primary step.
TlCl3 + 2 LiPPh2 ® TlCl + Ph2P±PPh2 + 2 LiCl
(4)
4
This oxidation reaction can be generalized. The disilyl
-
t
organoarsane BuAs(SiMe3)2 is the starting compound
for the formation of the bicyclic octaarsane
(tBuAs)3As±As(AstBu)3, first sythesized and struc-
turally characterized by Fenske et al. [24] [Gl. (5)].
TlCl3 THF
TlCl Me3SiCl
tBuAs(SiMe3)2
(tBuAs)3As±As(AstBu)3
(5)
5
1±5 are airsensitive colorless solids. The 1H NMR
t
spectra of 1 show only one signal for the Bu group at
1.21 ppm. Although it is possible to crystallize a di-
meric and a trimeric modification, the predominating
oligomer in solution is the dimer verified by cryo-
scopic measurements in benzene. VT-NMR investiga-
tions exhibit no evidence for other oligomers as could
i
be shown for indium phosphides such as Pr2InPPh2
Z. Anorg. Allg. Chem. 1999, 625, 954±960
955

A. Dashti-Mommertz, B. NeumuÈller
Fig. 1 Computer-generated plot of the dimeric unit [1]2
(SHELXTL [45], ellipsoids at the 50% probability level, H
atoms omitted for clarity).
Fig. 3 Structure of the dianion [(GaCl2)6(AstBu)4]2± in
3 ´ THF.
Fig. 2 Structure of the dianion [(InCl)4(InCl2)2(AstBu)6]2±
in 2.
Scheme 1 a) Part of the wurtzite structure. b) Asterane
structure of [Cl2Si(CH)2(SiCl)2CH2]2 [29]. c) Basic skeleton
in [RMER']6 [20, 30±32]. d) In6As6 backbone of
[(InCl)4(InCl2)2(AstBu)6]2± in 2. e) Part of the zinc blende
structure. f) Ga6As4 backbone of [(GaCl2)6(AstBu)4]2± in
3 ´ THF.
[Me2InAsMe2]2 [27] are 267±271 pm depending on the
substituents. The largest deviation from a mean plane
of the atoms In1, As2, In3 and As3 is 8 pm. With an
average value of 249 pm the In±Cl bond lengths are
somewhat longer than typical terminal In±Cl bonds
containing indium centers with CN (coordination
number) four [28]. Asterane structures in inorganic
chemistry are known by the work of Fritz et al. [29].
The carbosilane [Cl2Si(CH)2(SiCl)2CH2]2 is one of the
examples; it was obtained by the pyrolysis of
Me2SiCl2 [29 b, 29 c]. The asterane-like structure of
the dianion in 2 can be derived from the wurtzite
structure (Scheme 1) as well as the recently published
cage compounds [HMER]6 [20], while the basic struc-
tural motif of the adamantane-like dianion of 3 ´ THF,
[(GaCl2)6(AstBu)4]2±, is the zinc blende structure (Fig
-
ure 3, Scheme 1). The reason for the domination of
the wurtzite type in organometal chemistry is mainly
956
Z. Anorg. Allg. Chem. 1999, 625, 954±960

Gallium and Indium Arsanido Metalates
Experimental Section
All experiments were carried out under an atmosphere of
argon with Schlenk techniques. Purification and drying of
the organic solvents were performed by standard methods
[40]. MCl3 (M = Ga [41], In [41], Tl [42]), LiPPh2, LiAstBu2
and Li2AstBu [43] were prepared following literature proce-
dures.
1H, 13C and 31P NMR spectra were recorded on a Bruker
AC-300 spectrometer (1H: 300.133 MHz, 13C: 75.469 MHz,
31P: 202.456 MHz). TMS (1H, 13C) and 85% aqueous H3PO4
(31P) were used as external standard, d = 0.0. IR spectra
were obtained with a Bruker IFS-88 (nujol mulls, CsI discs
for the range 4000±500 cm±1; polyethylen discs for the range
500±100 cm±1). For the EI mass spectra a Varian CH 7 a
mass spectrometer (70 eV) was used. Melting points (uncor-
rected) were determined with a Dr. Tottoli (BuÈchi) melting-
point apparatus in sealed capillaries under argon. The cryo-
scopic measurements were performed with a Normag mole-
cular weight determination apparatus equipped with a Beck-
mann thermometer under argon.
Fig. 4 Computer-generated plot of
a molecule of
Ph2P±PPh2.
Cl2InAstBu2 (1). To a suspension of 0.33 g (1.49 mmol) InCl3
in 10 mL of THF 0.3 g (1.53 mmol) of LiAstBu2 in 10 mL of
THF was added dropwise at ±78 °C. The now orange solu-
tion was stirred for 3 h at ±79 °C and 2 d at 20 °C. The solu-
tion was evaporated under vacuum and the residue was trea-
ted with 10 mL of toluene and filtered. The product
precipitated at ±25 °C.
Yield: 0.85 g (66%, based on InCl3); m.p. 121 °C.
Elemental analysis: C8H18AsCl2In (374.88): calcd C 25.63,
H 4.84, As 19.99, Cl 18.92; found C 25.81, H 4.90, As 20.13,
Cl 18.62%.
due to the domination of the 1 : 1 composition in the
derivatives [RM-ER'] shown e.g. in [(THF)MgNPh]6
[30], [LiNPPh3]6 [31] and [tBuGaS]6 [32]. The ada-
mantane-like type was found for example in
[(IAl)4(S)2(SMe)4] [33]. The thermodynamic stable
modification of GaAs and InAs at room temperature
is in both cases the zinc blende structure [34].
Although [(GaCl2)6(AstBu)4]2± possesses only nearly
Td symmetry the Ga±As distances vary only between
243.3(1) and 244.7(1) pm. The values are even shorter
than the bond lengths in gallium compounds with CN 3
at the gallium center such as tBu2GaAstBu2
[246.6(3) pm] [35] and tBu2GaAs(SiPh3)[CH(SiMe3)2]
[245.8(1) pm] [36]. Comparable Ga±As atom distances
were measured in [({(Me3Si)2CH}2Ga)3Ga2(AsPh2) ´
(AsPh){(H)AsPh}] [245.0(1)±255.3(1) pm] [18], in
[Br{(Me3SiCH2)2As}GaAs(CH2SiMe3)2]2 [terminal
1H NMR (CD3CN): 1.21 ppm (s, CCH3).
13C NMR (CD3CN): 34.9 ppm (CCH3), 55.0 ppm (CCH3).
IR (Nujol, cm±1): 2721 w, 1760 w, 1695 w, 1633 w, 1308 s, 1296 s, 1296 s,
1262 s, 1152 s, 1098 w, 1090 w, 1074 w, 1042 s, 1019 w, 966 w, 916 s, 887 s,
847 s, 801 m, 694 m, 673 m, 667 m, 644 w, 596 w, 590 w, 581 w, 558 w, 538 w,
527 w, 519 w, 494 w, 486 w, 477 w, 463 w, 430 w, 422 w, 415 w, 409 w, 327 s
(mInCl2), 250 m (mIn2As2), 208 w, 185 w. EI MS (70 eV), m/z (rel. Int. in
%): 300 (12) (ClInAs2)+, 225 (2) (ClInAs)+, 190 (2) (InAs)+, 168 (5)
(ClAsC4H9)+, 150 (10) (InCl)+, 115 (8) (In)+, 75 (3) (As)+, 57 (96)
(C4H9)+.
[Li(THF)4]2[(InCl)4(InCl2)2(AstBu)6] (2): 1.22 g (5.5 mmol)
InCl3 were suspended in 50 mL of Et2O at ±78 °C and 0.8 g
(5.5 mmol) of Li2AstBu in 20 mL of Et2O were added under
stirring. The color of the reaction mixture turned into red
during the warm-up to 20 °C and a pale brown solid precipi-
tated. The mixture was filtered and the filtrate was evapo-
rated to dryness. The residue was dissolved in THF. After
two weeks colorless needles precipitated at 20 °C.
Ga±As
bond:
243.7(1) pm]
[37]
and
in
[Br2GaAs(CH2SiMe3)2]3 (245 pm) [21].
4 consists of centrosymmetric molecules with an
antiperiplanar conformation (Figure 4). The two phe-
nyl rings enclose an angle of 80°. The value of the P±P
bond length of 221.7(1) pm is typical for diphosphanes
[38]. The antiperiplanar conformation is also present
in Me2P±PMe2 (P±P: 221.2(1) pm) [38 a] and in
Yield: 1.18 g (55%); m.p. 146 °C (dec.).
Elemental analysis: C56H118As6Cl8In6Li2O8 (2355.5):
calcd C 28.56, H 5.05, As 19.08, Cl 12.04, Li 0.59; found:
C 28.43, H 4.92, As 19.20, Cl 11.75, Li 1.17%
Mes2P±PMes2 with
a
long P±P distance of
226.0(1) ppm, caused by the bulk of the substituents
[38 b]. Gauche conformations have been observed in
(C6H11)2P±P(C6H11)2 (P±P: 221.5(3) pm) [38 c] and in
(tBu2P)2P±P(PtBu2)2 (P±P average: 222 pm) [38 d].
1H NMR (CD3CN): 1.82 ppm (m, 70 H, OCH2CH2, CCH3), 3.67 ppm (m,
16 H, OCH2CH3).
13C NMR (CD3CN): 26.2 ppm (OCH2CH2, THF), 31.2 ppm (CCH3,
tBuAsIn2), 34.9 ppm (CCH3, tBuAsIn3), 50.0 ppm (CCH3, tBuAsIn3),
51.4 ppm (CCH3, tBuAsIn2), 68.4 ppm (OCH2CH2, THF).
IR (Nujol, cm±1): 2722 w, 2670 w, 1630 w, 1603 m, 1312 w, 1262 m,
1209 m, 1179 m, 1150 m, 1040 s, 938 m, 914 m, 887 s, 881 s (sh), 754 m,
694 w, 675 w, 608 w, 559 w, 514 m, 465 m, 397 m, 316 s (mInCl), 281 m (sh,
mInCl2), 247 m (sh), 225 m (sh), 209 m (mIn6As6), 153 w.
There is no short intermolecular contact in
4
(P1 ´ ´ ´ P1b: 406.7(1) pm) as it was observed for the
higher homologes Sb and Bi [39]. This was expected
on account of the detailed study of Me2P±PMe2
(P ´ ´ ´ P: 381.3(1) pm) [38 a].
EI MS (70 eV), m/z (rel. Int. in %): 300 (12) (ClInAs2)+, 150 (7)
(InCl)+, 115 (12) (In)+, 75 (2) (As)+, 57 (43) (C4H9)+.
Z. Anorg. Allg. Chem. 1999, 625, 954±960
957

A. Dashti-Mommertz, B. NeumuÈller
Table 1 Crystal data, data collection and refinement parameters
[1]2
2
3 ´ THF
4
formula
Mr
crystal size/mm
a/pm
b/pm
c/pm
C16H36Cl4As2In2
749.75
C56H118As6Cl8In6Li2O8
2355.50
0.15 ´ 0.15 ´ 0.077
1471.7(1)
1551.4(1)
2033.3(2)
108.32(1)
4407.1(6)
P21/n
14
2
1.775
190
C52H108As4Cl12Ga6Li2O9
2034.75
0.3 ´ 0.44 ´ 0.22
1267.0(1)
2321.7(2)
2829.3(3)
90.77(1)
8322(1)
P21/n
14
4
1.624
190
C24H20P2
370.37
0.3 ´ 0.23 ´ 0.04
1252.2(1)
588.7(1)
1305.7(1)
94.56(1)
959.5(2)
P21/n
14
2
1.282
190
0.22 ´ 0.22 ´ 0.12
874.2(1)
1173.1(1)
1324.3(1)
95.35(1)
1352.2(3)
I2/m
12
2
1.841
190
b/°
V/pm3 ´ 106
space group
No. [47]
Z
qcalc/gcm±1
T/K
abs. corr.
l
numerical
45.3
numerical
40.6
numerical
39.2
numerical
2.3
MoKa/cm±1
2hmax/°
51.82
51.77
52.0
51.8
h, k, l
±10 £ h £ 10
±14 £ k £ 14
±16 £ l £ 16
5329
1384
0.0364
±17 £ h £ 15
±18 £ k £ 15
±24 £ l £ 24
34321
8488
0.0552
±15 £ h £ 15
±28 £ k £ 28
±34 £ l £ 34
62991
16175
0.0849
±15 £ h £ 15
±7 £ k £ 7
±16 £ l £ 14
6089
1835
0.062
measured refl.
unique refl.
Rint
refl. Fo > 4r(Fo)
1205
61
5839
398
7326
794
1119
119
0.0502
0.1292f)
0.92/±0.27
parameters
a)
R1
0.0594
0.0372
0.0469
wR2b) (all data)
0.1868c)
1.43/±1.02
0.0834d)
0.95/±0.47
0.0904e)
0.59/±0.43
max./min. residue
electron density/epm±3 ´ 106
R1 = R||Fo| ± |Fc||/R|Fo|. b) wR2 = [Rw(F2o ± F2c )2/Rw(F2o)2]1/2 c) w = 1/[r2(F2o) + (0.0982 ´ P)2 + 70.16 ´ P] and P = [max(Fo2, 0) + 2 F2c]/3.
.
a)
d) w = 1/[r2(Fo2 ) + (0.0456 ´ P)2]. e) w = 1/[r2(Fo2 ) + (0.039 ´ P)2]. f) w = 1/[r2(F2o) + (0.0759 ´ P)2].
1H NMR (C6D6): 6.9±8.0 ppm (m, phenyl-H).
[Li(THF)4]2[(GaCl2)6(AstBu)4] ´ THF (3 ´ THF): 1.33 g
(9.1 mmol) of Li2AstBu in 30 mL of Et2O were added
dropwise to 2.42 g (13.7 mmol) of GaCl3 in 20 mL Et2O at
±78 °C. The yellow reaction mixture was warmed up to 20 °C
and evaporated to dryness. The residue was suspended in to-
luene/THF, filtered and stored at 20 °C. Colorless crystals
precipitated after three days. Yields: 3.09 g (67%); m.p.
136 °C (dec.).
Elemental analysis: C52H108As4Cl12Ga6Li2O9 (2034.75):
calcd C 30.7, H 5.35, Ga 20.56, As 14.73, Li 0.68, Cl 20.91;
found C 30.45, H 5.21, Ga 21.03, As 14.74, Li 0.64,
Cl 21.31%.
13C NMR (C6D6): 127.2 ppm (d, 3J(PC) = 9.1 Hz, C3/5), 130.0 ppm (d,
1J(PC) = 10.1 Hz, C1), 133.4 ppm (s, C4), 133.5 ppm (d, 2J(PC) = 25.7 Hz,
C2/6).
31P NMR (C6D6): ±13.6 ppm.
IR (Nujol, cm±1): 2722 w, 2667 w, 2335 w, 1953 w, 1880 w, 1807 w, 1655 w,
1583 w, 1567 m, 1330 m, 1304 m, 1260 m, 1178 m, 1159 m, 1088 m, 1067 vw,
1022 m, 997 m, 962 w, 917 w, 864 m, 848 m, 796 m, 689 m, 550 w, 526 w,
514 w, 495 s, 457 m, 438 w, 415 w, 392 m, 308 w, 249 w, 221 w.
EI MS (70 eV), m/z (rel. Int. in %): 370 (22) M+, 216 (1) (M±2Ph)+,
185 (33) (M/2)+, 108 (100) (PPh)+, 77 (17) (Ph)+.
[As(AstBu)3]2 (5): A solution 1.5 g (4.5 mmol) of TlCl3 in
50 ml of THF was added to 1.34 g (4.8 mmol) of
tBuAs(SiMe3)2 in 10 mL of THF. The color of the reaction
mixture turned to yellow and a solid precipitated. The mix-
ture was filtered and the filtrate was stored at 5 °C. Colorless
needles of 5 precipitated during one week. Yield: 0.32 g
1H NMR (CD3CN): 1.92 ppm (s, 36 H, CCH3), 1.95 ppm (s, 20 H,
OCH2CH2, THF), 3.76 ppm (s, 20 H, OCH2CH2, THF).
13C NMR (CD3CN): 24.9 ppm (OCH2CH2, THF), 34.2 ppm (CCH3),
50.8 ppm (CCH3), 67.1 ppm (OCH2CH2, THF).
t
(56%, based on BuAs(SiMe3)2); m.p. 117 °C.
IR (Nujol, cm±1): 2726 w, 1345 s, 1307 m, 1294 m, 1261 m, 1153 m,
1079 s, 1042 s, 918 m, 803 w, 669 m, 584 m, 516 w, 485 m, 450 m, 435 m,
390 m, 378 m, 331 s (mGaCl2), 295 s (mGaCl2), 247 s (mGa6As4), 224 m,
191 m, 140 m, 112 m.
Elemental analysis: C24H54As8 (942.05): calcd C 30.60,
H 5.78, As 63.62; found C 30.90, H 5.94, P 64.00%.
1H NMR (C6D6): 1.37 ppm (s, 9 H, CCH3), 1.38 ppm (s, 18 H, CCH3).
13C NMR (C6D6): 29.9 ppm (3 C, CCH3), 30.8 ppm (6 C, CCH3),
47.4 ppm (1 C, CCH3), 50.9 ppm (2 C, CCH3).
EI MS (70 eV), m/z (rel. Int. in %): 300 (6) [Ga2As(C4H9)2]+, 283 (2)
(Ga2Cl2As)+, 208 (20) (Ga2Cl2)+, 174 (3) (GaCl3)+, 139 (15) (GaCl2)+,
133 (1) (HGaC4H9)+, 75 (1) (As)+, 72 (25) (THF)+, 69 (3) (Ga)+, 57 (12)
(C4H9)+.
IR (Nujol, cm±1): 2708 w, 1361 m, 1260 m, 1157 s, 1073 m, 1011 m, 892 m
(br), 803 s, 621 w, 519 w, 391 m, 347 m, 290 m, 224 m, 150 w.
EI MS (70 eV), m/z (rel. Int. in %): 885 (13) [M±(C4H9)]+, 471 (29)
[As4(C4H9)3]+, 415 (57) [HAs4(C4H9)2]+, 300 (23) (As4)+, 75 (9) (As)+,
57 (100) (C4H9)+.
Ph2P±PPh2 (4): A suspension of 0.8 g (4.22 mmol) LiPPh2 in
50 mL of toluene was added dropwise to 0.65 g (2.11 mmol)
of TlCl3 in toluene at 20 °C. A colorless solid precipitated.
The mixture was stirred for 3 h at 20 °C and then filtered.
The filtrate was evaporated to 5 mL. Tiny needles of 4 preci-
pitated after one month. Yield: 0.35 g (45%); m.p. 80 °C.
Elemental analysis: C24H20P2 (370.37): calcd C 77.83,
H 5.44, P 16.73; found C 77.6, H 5.31, P 16.61%.
X-ray structure analyses of [1]2±4: The crystals were covered
with a high boiling paraffin oil and mounted on the top of a
glass capillary under a flow of cold gaseous nitrogen. The or-
ientation matrix and preliminary unit cell dimensions were
determined from 2000 reflections with a IPDS system (Stoe;
958
Z. Anorg. Allg. Chem. 1999, 625, 954±960

Gallium and Indium Arsanido Metalates
Table 2 Selected bond lengths/pm and angles/° in [1]2, 2, 3 ´ THF and 4
[1]2
In1±As1
In1±Cl1
In1±Cl2
As1±C1
265.2(1)
245.4(2)
245.9(2)
201(1)
As1±In1±As1 a
In1±As1±In1 a
As1±In1±Cl1
As1±In1±Cl2
Cl1±In1±Cl2
C1±As1±C1 a
89.95(4)
90.05(5)
115.98(5)
115.04(5)
104.99(9)
115.1(5)
2
In1±As1
In1±As2
In1±As3
In1±Cl1
In2±As2
In2±Cl2
In2±Cl3
In2±As3 a
In3±As2
In3±As3
In3±Cl4
In3±As1 a
258.29(8)
267.58(8)
266.42(7)
250.3(4)
260.21(8)
247.6(4)
246.8(6)
259.63(8)
267.26(8)
268.29(8)
250.1(4)
258.86(8)
As1±In1±As2
As1±In1±As3
As2±In1±As3
As2±In2±As3 a
As2±In3±As3
As2±In2±As1 a
As3±In3±As1 a
In1±As1±In3 a
In1±As2±In3
In2±As2±In3
In1±As3±In3
In1±As3±In2 a
In3±As3±In2 a
125.40(3)
115.94(3)
88.63(2)
107.40(3)
88.30(2)
115.26(3)
126.43(3)
97.17(3)
91.13(2)
107.25(3)
91.16(2)
106.86(3)
114.78(3)
3 ´ THF
Ga1±As1
Ga1±As2
Ga2±As1
Ga2±As3
Ga3±As1
Ga3±As4
Ga4±As2
Ga4±As3
Ga5±As3
Ga5±As4
Ga6±As2
Ga6±As4
244.1(1)
244.0(1)
244.5(1)
244.4(1)
244.57(9)
244.7(1)
243.91(9)
244.7(1)
244.4(1)
244.0(1)
243.4(1)
243.3(1)
As1±Ga1±As2
As1±Ga2±As3
As1±Ga3±As4
As2±Ga4±As3
As3±Ga5±As4
As2±Ga6-As4
Ga2±As3±Ga4
Ga2±As3±Ga5
Ga4±As3±Ga5
Ga3±As4±Ga5
Ga3±As4±Ga6
Ga5±As4±Ga6
110.09(4)
109.63(4)
108.09(3)
109.74(4)
110.43(4)
109.67(4)
109.65(4)
107.30(4)
109.95(4)
110.63(4)
110.27(4)
108.06(4)
Ga1±As1±Ga2
Ga1±As1±Ga3
Ga2±As1±Ga3
Ga1±As2±Ga4
Ga1±As2±Ga6
Ga4±As2±Ga6
111.88(4)
107.73(4)
109.29(4)
108.84(4)
108.10(4)
110.86(4)
4
P1±P1 a
P1±C1
P1±C2
221.7(1)
184.3(3)
185.8(3)
C1±P1±C2
C1±P1±P1 a
C2±P1±P1 a
P1±C1±C11
P1±C1±C15
P1±C2±C21
P1±C2±C25
98.3(1)
100.9(1)
99.1(1)
127.0(2)
115.1(2)
118.2(2)
122.7(2)
graphite-monochromated MoKa radiation, k = 71.073 pm).
The final cell parameters were determined with 5000 re-
flections. The intensities were corrected for Lorentz and po-
larization effects (for cell parameters and intensity collection
see Table 1). The structures were solved by direct methods
with the programs SHELXTL-Plus [44] ([1]2, 2, 4) and
SHELXTL [45] (3 ´ THF). The positions of the hydrogen
atoms were calculated for ideal positions and refined with a
common displacement parameter. Two THF molecules in 3
and one in 3 ´ THF are disordered. In 2 six split positions
(C521, C522; C571, C572; C641, C642; occupation factor:
0.5) and in 3 ´ THF two split positions (C831, C832; occupa-
tion factors: 0.6, 0.4) could be refined.
The calculation of the bond lengths, bond angles and Ueq
was performed by the program PLATON [46]. Further de-
tails of the crystal structure investigations may be obtained
from the Fachinformationsdienst Karlsruhe, D-76344 Eggen-
stein-Leopoldshafen (Germany) on quoting the depository
numbers CSD-410516 ([1]2), CSD-410517 (2), CSD-410518
(3 ´ THF) and CSD-410519 (4).
Acknowledgement: We thank the Fonds der Chemischen
Industrie for financial support.
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