Synthesis and crystal structures of aluminum, gallium and indium complexes with chelating Me2Si(NPh)22- ligands

Article abstract of DOI:10.1002/zaac.201100371

The reaction of ECl₃ (E = Al, Ga) with two equivalentsof Li ₂Me₂Si(NPh)₂ (in diethyl ether/n-hexane) leads to the formation of bis-chelate complexes [Li(OEt₂) ₃][E{Me₂Si(NPh)₂}₂] (E = Al (1), Ga (2)). Compounds 1 and 2 crystallize isotypically in the monoclinic system with a = 1136.42(6), b = 3267.9(1), c = 1360.37(8) pm, β = 94.320(7)° for 1 and a = 1140.88(6), b = 3261.7(2), c = 1360.20(8) pm, β = 94.641(7)° for 2. Both the compounds display a distorted tetrahedral coordination of the central metal atom to give a spirocyclic EN₄Si₂ core. The Al-N bond lengths are in the range of186.5-186.9 pm and for the Ga-N distances values between 192.3and 193.1 pm are observed. Treatment of InCl₃ with three equivalents of Li₂Me₂Si(NPh)₂ yields the tris-chelate [{Li(OEt₂)}₃In{Me₂Si(NPh ₂)}₃] 3. Compound 3 crystallizes in the trigonal crystal system, space group R3c with a = 1852.4(1), and c = 3300.2(2) pm. The central indium atom is coordinated by threeMe₂Si(NPh) ₂^2- ligands in a distorted octahedral arrangement withIn-N bond lengths of 230.8 pm. Copyright

Full text of DOI:10.1002/zaac.201100371

ARTICLE
DOI: 10.1002/zaac.201100371
Synthesis and Crystal Structures of Aluminum, Gallium and Indium
2–
Complexes with Chelating Me2Si(NPh)2 Ligands
Ankush Mane,[a] Christoph Wagner,[a] and Kurt Merzweiler*[a]
Keywords: Aluminum; Gallium; Indium; Silyl amides; Crystal Structure
Abstract. The reaction of ECl3 (E = Al, Ga) with two equivalents 186.5–186.9 pm and for the Ga–N distances values between 192.3
of Li2Me2Si(NPh)2 (in diethyl ether/n-hexane) leads to the formation and 193.1 pm are observed. Treatment of InCl3 with three equi-
of bis-chelate complexes [Li(OEt2)3][E{Me2Si(NPh)2}2] (E = Al (1), valents
of
Li2Me2Si(NPh)2
yields
the
tris-chelate
Ga (2)). Compounds 1 and 2 crystallize isotypically in the monoclinic [{Li(OEt2)}3In{Me2Si(NPh2)}3] 3. Compound 3 crystallizes in the tri-
¯
system with a = 1136.42(6), b = 3267.9(1), c = 1360.37(8) pm, β =
94.320(7)° for 1 and a = 1140.88(6), b = 3261.7(2), c = 1360.20(8)
pm, β = 94.641(7)° for 2. Both the compounds display a distorted
gonal crystal system, space group R3c with a = 1852.4(1), and c =
3300.2(2) pm. The central indium atom is coordinated by three
Me2Si(NPh)2 ligands in a distorted octahedral arrangement with
2–
tetrahedral coordination of the central metal atom to give a spiro- In–N bond lengths of 230.8 pm.
cyclic EN4Si2 core. The Al–N bond lengths are in the range of
Introduction
Results and Discussion
2–
Reaction of ECl3 (E = Al, Ga) with two equivalents of Li2-
Me2Si(NPh)2 leads to the formation of the bis-chelate com-
plexes [Li(OEt2)3][E{Me2Si(NPh)2}2] (E = Al: 1, Ga: 2) ac-
cording to Equation (1). In the case of InCl3 the reaction re-
quires three equivalents of the silyldiamide and consequently
the tris-chelate [{Li(OEt2)}3In{Me2Si(NPh)2}3] (3) is formed
(Equation (2)).
Silyldiamides of the type R2Si(NRЈ)2 are versatile ligands
for the synthesis of complexes of main group and transition met-
als. About 30 years ago silyldiamides have started to play a key
role in the investigation of low-valent main group element com-
pounds, like in the case of the Veith-stannylene Me2Si(NtBu)2-
Sn.[1] Moreover, silyldiamides are valuable building blocks for
the synthesis of group 13 and group 14 cluster compounds
like
[{Me2Si(NtBu)2}2(OtBu)2Al2],[2]
[{Me2Si(NtBu)2}2-
(NtBu)2(GaMe)2],[3]
[Li{Me2Si(NSiMe3)2}2In],[4]
[{Me2Si(NtBu)2}2Ge2E2}] (E = S, Se, Te],[5] [{Me2Si(NtBu)2}2-
Sn2(OtBu)Cl],[6] [{C3H6Si(NtBu)2}2Pb2].[7] Like in the case of
the main group elements numerous examples of transition metal
complexes with chelating silylamide ligands have been de-
scribed. Since the first reports on titanium, zirconium and haf-
nium compounds [M{Me2Si(NtBu)2}2] by Bürger et al. (M = Ti,
Zr,[8] Hf[9]) research on metal silylamides is developing continu-
ously. For example, most recent results have shown that steri-
cally encumbered silylamides can be used as supporting ligands
in dinuclear complexes with Zn–Zn bonds.[10] Additionally there
is an increasing interest in silylamide derivatives with lanthano-
ids, like [Li(thf){Me2Si(NPh)2}2Yb(thf)2].[11]
(1)
(2)
Compounds 1–3 and LiCl are precipitated from the reaction
mixture to give a grey solid. After filtration the residue is ex-
tracted with toluene/diethyl ether to dissolve 1–3. Storage of
the filtrate at –25 °C leads to the formation of colorless, air
and moisture sensitive crystals of 1·toluene, 2·toluene and 3 in
yields around 80%.
The 29Si NMR spectra of the compounds 1–3 consist of sin-
glet signals at similar shifts (1: –4.2 ppm, 2: –11.6 ppm, 3:
–11.3 ppm). In the proton NMR spectra of the compounds 1
This paper deals with the synthesis and characterization of
novel anionic aluminum, gallium, and indium chelate com-
2–
plexes with Me2Si(NPh)2 ligands.
* Prof. Dr. K. Merzweiler
E-mail: kurt.merzweiler@chemie.uni-halle.de
[a] Institut für Chemie
2–
Kurt Mothes-Str. 2
and 2 signals of the Me2Si(NPh)2 ligand, diethyl ether and
Naturwissenschaftliche Fakultät II
Martin-Luther-Universität Halle-Wittenberg
06120 Halle, Germany
toluene are observed with relative intensities of 2:3:1. The
2–
NMR spectrum of 3 displays the signals of the Me2Si(NPh)2
136
© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2012, 638, (1), 136–140

2–
Al, Ga and In Complexes with Chelating Me2Si(NPh)2 Ligands
ligands and the coordinated OEt2 molecule with relative inten- minum coordinated tetrahedrally by four monodentate amide
ligands. The N–Al–N angles are in the range of 82.0 to
130.6(1)°. As a consequence of the formation of four-mem-
bered AlN2Si chelate rings the N–Al–N angles deviate signifi-
cantly from the values in an ideal tetrahedron. This leads to
acute endcocyclic angles of 82.0(1) and 82.1(1)° for N(1)–Al–
N(2) and N(3)–Al–N(4). The remaining exocyclic N–Al–N
angles are obtuse, ranging from 121.9(1)° to 130.6(1)°. A sim-
ilar distortion has been observed in the titanium chelate com-
plex [Ti{Me2Si(NtBu)2}2] with two acute N–Ti–N angles of
83.3 and 83.6° within the SiN2Ti chelate rings and four obtuse
exocyclic N–Ti–N angles of 122.9–127.8°.[8] The geometric
parameters of the Me2Si(NPh)2 units in complex 1 are very
similar to those observed in Me2Si(NHPh)2.[14] The Si–N bond
lengths remain essentially unchanged (172.8–173.8 pm vs.
172.3–174.0 pm) and in the case of the N–Si–N angle a small
reduction (90.0° vs. 111.3°) due to the steric requirements of
the four membered Si2N2Al ring is observed. Spirocyclic alu-
minum compounds containing bisamide chelate ligands X(NR)2
are rare. Some recent examples reported by Chivers et al. com-
prise the O2S(NtBu)2 and PhB(NtBu)2 derivatives Na(15-
crown-5)[{O2S(NtBu)2}2Al], Li(thf)2)[{O2S(NtBu)2}2Al][15]
and [{PhB(NtBu)2}2Al].[16] Like in the case of compound 1 a
bisphenoidal distortion of the AlN4 coordination tetrahedron is
sities of 1:1. Compared to the starting compound Me2Si-
(NHPh)2 the signals of the Me2Si groups in compounds 1–3
display a small downfield shift of approx. 0.4–0.6 pm and for
the CH2 and CH3 signals of the diethyl ether molecules a small
upfield shift in the range of 0.3–0.5 ppm compared to uncoor-
dinated diethyl ether is observed.
Crystal Structures
Details of the crystal structure determinations are collected
in Table 1. Compounds 1 and 2 are crystallizing isotypically
in the monoclinic crystal system, space group P21/n with one
molecule of toluene per formula unit. Both compounds consist
of discrete [Li(OEt2)3]+ cations and [E{Me2Si(NPh)2}2]–
anions (E = Al, Ga) with no unusual short contacts.
The [Al{Me2Si(NPh)2}2]– anion (Figure 1) consists of an
aluminum atom which is coordinated nearly tetrahedrally by
two chelating Me2Si(NPh)2 units to give a spirocyclic Si2N4Al
core. The Al–N bond lengths are in a narrow range of 186.5(2)
to 186.9(2) pm. Similar Al–N bond lengths of have been ob-
served for tetrakis(3,5-dimethylpyridine)-lithium tetrakis(3,5-
dimethyl-1,4-dihydropyridyl)-aluminum(III)
(185.6 pm)[12]
and [(thf)2LiAl(NMe2)4] (183.6–190.6 pm)[13] containing alu- observed.
Table 1. Crystallographic data and details of the crystal structure refinement for 1·toluene, 2·toluene and 3.
Empirical formula
C47H70AlLiN4O3Si2
829.17
C47H70GaLiN4O3Si2
C54H78InLi2N6O3Si3
1079.13
Formula weight
Temperature /K
Wavelength /pm
Crystal system
871.92
220(2)
71.073
monoclinic
P21/n
monoclinic
P21/n
trigonal
¯
Space group
R3c
Unit cell dimensions /pm,°
a = 1136.42(6)
b = 3267.9(1)
c = 1360.37(8)
α = 90
1140.88(6)
3261.7(2)
1360.20(8)
90
1852.4(1)
1852.4(1)
3300.2(2)
90
β = 94.320(7)
γ = 90
94.641(7)
90
90
120
Volume /pm3
Z
5037.7(4) ϫ 106
4
5045.0(5) ϫ 106
4
9807.5 ϫ 106
6
Calculated density /g·cm–3
Absorption coefficient /mm–1
Crystal size /mm
1.093
0.128
0.76 ϫ 0.30 ϫ 0.26
1.9–24.95°
–13 Յ h Յ 13,
–37 Յ k Յ 38,
–16 Յ l Յ 16
33186/8683
[R(int) = 0.0515]
Full-matrix least-squares on F2
8683/0/535
1.048
1.147
0.633
1.103
0.459
0.44 ϫ 0.40 ϫ 0.38
2.18–25.00°
–13 Յ h Յ 13
–38 Յ k Յ 34,
–16 Յ l Յ 16
28294/8296
[R(int) = 0.0456]
0.30 ϫ 0.30 ϫ 0.30
2.87–25.91°
–22 Յ h Յ 22
–22 Յ k Յ 22
–40 Յ l Յ 40
24130/2112
[R(int) = 0.0350]
Θ range for data collection
Limiting indices
Reflections collected / unique
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [IϾ2σ (I)]
8296/0/523
1.035
0.0480
2112/0/113
1.214
0.033
R1 = 0.057
wR2 = 0.1515
R1 = 0.088
0.1209
0.068
0.1322
0.0397
R indices (all data)
wR2 = 0.1682
0.630/–0.344
834859
0.1335
0.611/–0.332
834860
0.1377
0.946/–0.390
834861
Largest diff. peak/hole/e·Å–3
CCDC
Programs used
SIR97,[22] SHELX,[23] DIAMOND[24]
Crystallographic data have been deposited with the Cambridge Crystallographic Data Centre. Copies of these data can be obtained free of
charge from the Cambridge Crystallographic Data Centre on application to the Director, CCDC, 12, Union Road, Cambridge CB2 1 EZ, UK
(E-mail: deposit@ccdc.cam.uk).
Z. Anorg. Allg. Chem. 2012, 136–140
© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
137

A. Mane, C. Wagner, K. Merzweiler
ARTICLE
Figure 1. Molecular structure of the [Al{Me2Si(NPh)2}2]– anion (a)
and the [Li(OEt2)3]+ cation (b) in 1. (Thermal ellipsoids are shown at
the 50% probability level). Selected bond lengths /pm and angles /°:
N(1)–Si(1) 173.8(2), N(1)–Al 186.9(2), N(2)–Si(1) 173.1(2), N(2)–Al
186.5(2), N(3)–Si(2) 173.7(2), N(3)–Al 186.5(2), N(4)–Si(2) 172.8(2),
N(4)–Al 186.6(2), N(3)–Al–N(2) 123.7(1), N(3)–Al–N(4) 82.1(1),
N(2)–Al–N(4) 121.9(1). N(3)–Al–N(1) 130.6(1), N(2)–Al–N(1)
82.0(1), N(4)–Al–N(1) 122.2(1), N(2)–Si(1)–N(1) 89.8(1), N(4)–
Si(2)–N(3) 90.0(1), S(1)–N(1)–Al, 93.8(1), i(1)–N(2)–Al 94.2(1),
Si(2)–N(3)–Al 93.8(1), Si(2)–N(4)–Al 94.1(1), Li–O1 192.6(5), Li–O2
191.3(6), Li–O3 190.3(5), O1–Li–O2 121.0(2), O2–Li–O3 120.5(3),
O1–Li–O3 118.3(3).
Figure 2. Molecular structure of the [Ga{Me2Si(NPh)2}2]– anion in 2.
(Thermal ellipsoids are shown at the 50% probability level). Selected
bond lengths /pm and angles /°: N(1)–Si(1) 172.2(3), N(1)–Ga
192.9(2), N(2)–Si(1) 173.2(2), N(2)–Ga 192.3(2), N(4)–Si(2) 171.4(3),
N(4)–Ga 193.1(2), N(3)–Si(2) 173.8(3), N(3)–Ga 192.4(3), N(2)–Ga–
N(3) 132.7(1), N(2)–Ga–N(1) 79.4(1), N(3)–Ga–N(1) 125.4(1), N(2)–
Ga–N(4) 123.8(1), N(3)–Ga–N(4) 79.6(1), N(1)–Ga–N(4) 122.7(1),
N(1)–Si(1)–N(2) 90.9(1), N(4)–Si(2)–N(3) 91.2(1), Si(1)–N(1)–Ga
94.8(1), Si(1)–N(2)–Ga 94.7(1), Si(2)–N(4)–Ga 94.8(1), Si(2)–N(3)–
Ga 94.3(1).
The [Li(OEt2)3]+ cation in compound 1 consists of a lithium from coordination number four in compounds 1 and 2 to six
atom coordinated by three diethyl ether molecules in a dis- in compound 3 is probably favored by the larger atomic radius
torted trigonal planar manner. The Li–O distances of 190.3(5) of indium compared to aluminum and gallium. In contrast to
to 192.6(2) pm and the O–Li–O angles of 118.3(3) to 121.0(3)° the complexes 1 and 2, which contain discrete [Li(OEt2)3]+
agree well with the geometrical values observed in other com- cations and [E{Me2Si(NPh)2}2]– anions, the Li(OEt2) units in
pounds with [Li(OEt2)3]+ cations, e.g. [Li(OEt2)3][Ti{S-2,4,6- compound 3 are in close contact with the chelate complex
iPrC6H2}4].[17]
[In{Me2Si(NPh)2}3]3–.
Compared to compound 1 the gallium derivative
exhibits a very similar structure composed of spirocyclic space group R3c. The indium atom resides on a special posi-
[{Me2Si(NPh)2}2Ga]– anions and [Li(OEt2)3]+ cations (Fig- tion (6a) with crystallographic D3 site symmetry. The coordi-
2
Compound 3 crystallizes in the trigonal crystal system,
¯
2–
ure 2). The main structural difference between compound 1 nation sphere around indium consists of three Me2Si(NPh)2
and the gallium derivative 2 arises from the larger metal ligands forming an nearly octahedral arrangement of six nitro-
nitrogen bond lengths (192.4(2)–193.1(2) pm vs. 186.5(2)– gen atoms. There are six In–N distances of 230.5(2) pm which
186.9(2) pm) due to the larger ionic radius of gallium. Conse- are equivalent by symmetry.
quently the endocyclic N–Ga–N angles are smaller (79.4(1)
The observed deviation from ideal octahedral coordination
2–
and 79.6(1)°] and the exocyclic N–Ga–N angles are larger arises mostly from the small “bite angles” of the Me2Si(NPh)2
(122.7(1)–132.7(1)°] than in compound 1. With respect to the ligands that causes N–In–N angles of 67.6(1)°. The remaining
Me2Si(NPh)2– ligands a small decrease of the Si–N bond cis N–In–N angles within the distorted octahedron are in the
lengths and a small increase of the N–Si–N angles compared range of 86.3(1) and 103.5(1)° and the trans N–In–N angles
to compound 1 is observed. The Ga–N bond lengths observed amount to 168.3(1)°. The lithium cations are coordinated by
2–
in compound 2 are close to the values that have been reported two nitrogen atoms of adjacing Me2Si(NPh)2 ligands and an
for [Li(thf)4][Ga{N(CH2Ph)2)}4] (189.2–192.5 pm).[18] Like in additional molecule of diethyl ether in a distorted trigonal
2–
the case of the spirocyclic aluminum chelates analogous gal- manner. This arrangement of three Me2Si(NPh)2 ligands and
lium derivatives containing X(NR)2 bisamide ligands are also three lithium cations leads to a puckered twelve-membered
rare. In 2005 Chivers et al. reported on [Ga{PhB(NtBu)2}2], Si3N6Li3 ring centered by an indium cation.
2–
which is isostructural to the aluminum derivative
[Al{PhB(NtBu)2}2].[16]
Indium compounds containing chelating R2Si(NR)2 li-
gands are rare. One of the few examples is the compound
In contrast to the formation of the bis-chelate complexes 1 Li[In{Me2Si(NSiMe3)2}2] (4) which was reported by Veith et
and 2 the reaction of InCl3 with three equivalents of Li2Me2- al. in 1993.[4] However, compound 4 is more closely related
Si(NPh)2
leads
to
the
tris-chelate
complex to compounds 1 and 2 than to compound 3 as it contains a
[{Li(OEt2)}3In{Me2Si(NPh)2}3] (3) (Figure 3). The change spirocyclic Si2N4In core. The favored formation of the bis-
138
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© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2012, 136–140

2–
Al, Ga and In Complexes with Chelating Me2Si(NPh)2 Ligands
the larger ionic radius of gallium compared to aluminum the
GaN4 unit exhibits a more pronounced bisphenoidal distortion
than the AlN4 unit. In the solid state both the compounds are
isostructural. The reaction of InCl3 with the bis-amide requires
a
1:3 stoichiometry and consequently the tris-chelate
[{Li(OEt2)}3In{Me2Si(NPh)2}3] is obtained. Due to its larger
atomic radius indium prefers coordination number six. In con-
trast to the aluminum and gallium derivatives, which exist as
discrete ion pairs [Li(OEt2)3]+[E{Me2Si(NPh)2}2]– (E = Al,
Ga), there is a close interaction between the Li(OEt2)+ frag-
ments and the nitrogen atoms of the [In{Me2Si(NPh)2}3]3–
complex. This stronger interaction is probably favored by the
higher charge of the [{Me2Si(NPh)2}3In]3– complex compared
to the monoanionic [E{Me2Si(NPh)2}2]– units.
Experimental Section
General Considerations: All manipulations were conducted under an
atmosphere of dry argon using Schlenk techniques. The solvents used
were freshly distilled and free of oxygen and moisture. Hexane was
dried with LiAlH4, toluene and diethyl ether were dried with Na/
benzophenone. NMR spectra were recorded with a Varian Unity 500.
Figure 3. Molecular structure of 3. (Thermal ellipsoids are shown at
the 50% probability level). Selected bond lengths /pm and angles /°:
N–Si 172.9(3), N–Li 206.5(5), N–In 230.8(2), Si–Ni 172.9(3), O–Li
190.7(8), Li–Nii 206.5(5), N–In–Ni 67.7(1), N–In–Nii 86.4(1), N–In–
Niii 103.4(1), N–In–Niv 103.4(1), N–In–Nv 168.4(1), N–Li–Nii 99.8(3),
N–Si–Ni 96.1(2), Si–N–Li 106.3(1), Si–N–In 98.1(1), O–Li–N
130.1(2) symmetry codes: i: y + 1/3, x–1/3, –z + 1/6, ii: –x + 4/3,
–x+y + 2/3, –z + 1/6, iii: –x+y+1, –x + 1, z, iv: –y + 1, x–y, z, v: x –y
+ 1/3, –y + 2/3, –z + 1/6.
Elementary analyses were carried out with a LECO CHNS-932. Crys-
tals of compounds 1–3 easily loose solvents on exposure to an atmo-
sphere of dry argon. Due to this rapid decomposition the analyses are
of moderate quality.
[Li(OEt2)3][E{Me2Si(NPh)2}2]·toluene (1: E = Al, 2: M = Ga) and
[{Li(OEt2)}3In{Me2Si(NPh)2}3] (3)
chelate 4 is probably due to the larger steric demand of the
SiMe3 groups compared to the phenyl groups. Similar to 3
there is a close interaction of the lithium cation with the nitro-
gen atoms of the Me2Si(NSiMe3)22– ligand. The In–N distance
of 230.5(2) pm in 3 is significantly larger than in 4 (205.6–
222.3 pm). This is mainly a consequence of the higher coordi-
nation number of indium in complex 3 compared to 4. In other
To a suspension of Me2Si(NHPh)2 (1.45 g, 6.0 mmol) in n-hexane
(100 mL) a solution of nBuLi (4.8 mL, 2.5 m, 12 mmol) in n-hexane
was added and stirred for 12 h. The suspension of the lithiated si-
lylamine was cooled to 0 °C and a solution of ECl3 (E = Al, Ga,
3 mmol) in diethyl ether (10 mL) was added. After forming a clear
hexacoordinate
indium
complexes
with
bidentate solution an off-white precipitate consisting of LiCl and
Li[E{Me2Si(NPh)2}2] was obtained. The residue was filtered off, dried
and afterwards washed several times with a mixture of toluene (50 mL)
and diethyl ether (10 mL). Storage of the filtrate at –18 °C yielded
colorless crystals of [Li(OEt2)3][E{Me2Si(NPh)2}2]·toluene.
(monoanionic) N,N ligands, like tris(bis(pyrazolyl)borato)-in-
dium(III) (221.9–223.7 pm)[19] and tris(N,NЈЈ-diphenyltriazen-
ido)-indium difluorbenzene solvate (223.5–224.8 pm),[20] the
In–N bonds are slightly shorter than in 3. Compound 3 dis-
plays six symmetry equivalent N–Li distances of 206.5(5) pm.
This value lies within the typical range of N–Li distances
observed in lithium silylaminde compounds like
Li2[Me2Si(NtBu)2] (200.3–210.3 pm) [21]. A nearly identical
N–Li distance of 206.4(6) pm has been observed in
Li[In{Me2Si(NSiMe3)2}2] (4).[4]
Compound 3 was synthesized similarly from Me2Si(NHPh)2 (1.45 g,
6 mmol), nBuLi (4.8 mL, 2.5 m) and InCl3 (2 mmol).
[Li(OEt2)3][Al{Me2Si(NPh)2}2]·toluene
(1):
2.15 g
(87%),
C40H62AlLiN4O3Si2·toluene (829.2), calcd. C 68.1, H 8.5, N 6.8%,
1
found: C 67.2, H: 8.1, N: 6.1%. H NMR (C6D6): δ = 0.55 (s, 12 H
SiCH3), 0.77 (t 18 H CH3 Et2O), 1.98 (s, 3 H, CH3, toluene), 2.84 (q,
12 H, CH2 Et2O), 6.44–7.03 (br., 20 H, SiPh, toluene). 13C NMR
(C6D6): δ = 1.4 (SiCH3), 15.1 (Et2O), 65.7 (Et2O), 118.3 (Ph), 119.7
(Ph), 130.3 (Ph), 151.0 (Ph), 21.4 (toluene), 125.6 (toluene), 128.5
(toluene), 129.5 (toluene), 137.8 (toluene) 29Si NMR (C6D6): δ = –4.2
(s)
Conclusions
The reaction of AlCl3 with two equivalents of the bis-amide
Li2Me2Si(NPh)2 leads to the formation of the anionic chelate
complex [Al{Me2Si(NPh)2}2], which contains a spirocyclic
AlN4Si2 core. In the solid state [Li(OEt2)3][Al{Me2Si(NPh)2}2]
consists of discrete [Li(OEt2)3]+ cations and [Al{Me2Si-
(NPh)2}2]– anions. The reaction of the bis-amide with GaCl3
proceeds in a similar way to form [Li(OEt2)3][Ga{Me2Si-
(NPh)2}2]. Like in the case of the aluminum compound the
[Li(OEt2)3][Ga{Me2Si(NPh)2}2]·toluene
(2):
2.33 g
(89%):
C40H62GaLiN4O3Si2·toluene (871.9), calcd. C 64.7, H 8.1, N 6.4%,
1
found: C 63.5, H: 7.9, N: 6.1%. H NMR (C6D6): δ = 0.66 (s, 12H
SiCH3), 0.90 (t 18 H, CH3 Et2O), 2.10 (s, 3 H, CH3, toluene), 2.98 (q,
12 H, CH2 Et2O), 6.61–7.15 (br., 20H SiPh and toluene). 13C NMR
(C6D6): δ = 1.4 (SiCH3), 15.1 (CH3 Et2O), 65.7 (CH2 Et2O), 118.3
gallium derivative displays a spirocyclic GaN4Si2 core. Due to (Ph), 119.7 (Ph), 130.3 (Ph), δ = 151.0 (Ph), 21.4 (toluene), 125.6
Z. Anorg. Allg. Chem. 2012, 136–140
© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de 139

A. Mane, C. Wagner, K. Merzweiler
ARTICLE
(toluene), 128.5 (toluene), 129.5 (toluene), 137.8 (toluene). 29Si NMR
(C6D6): δ = –11.2 (s)
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Chem. 1986, 310, 317.
[{Li(OEt2)}3In{Me2Si(NPh)2}3] (3): 2.09 g (89%), C54H78InLi3-
[10] Y.-C. Tsai, D.-Y. Lu, J.-K. Hwang, Y.-M. Lin, J.-S. K. Yu, Chem.
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25, 2880.
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N6O3Si3 (1079.1), calc: C 60.1, H 7.3, N 7.8%, found: C 61.9, H 7.1,
N 7.3%. H NMR (C6D6): δ = 0.47 (m 18 H CH3 Et2O), 0.55 (s, 12H
1
SiCH3), 2.56 (m, 12 H, CH2 Et2O), 6.54–7.17 (br., 30H of SiPh) 13C
NMR (C6D6): δ = 2.5 (SiCH3), 13.7 (CH3 Et2O), 63.0 (CH2 Et2O),
117.0 (Ph), 122.6 (Ph), 130.0 (Ph), 153.7 (Ph). 29Si NMR (C6D6):
δ = –11.28
Acknowledgement
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The authors wish to thank the Cluster of Excellence on Nanostructured
Materials, Sachsen-Anhalt and the IMPRS at the Max-Planck-Institute
of Microstructure Physics, Halle for generous support of this work.
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Received: August 17, 2011
Published Online: November 4, 2011
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Z. Anorg. Allg. Chem. 2012, 136–140