Syntheses and reactions of Saltren-Group 13 complexes

Article abstract of DOI:10.1016/S0022-328X(98)00544-0

Neutral Group 13 combinations with the Saltren ligand (tris(((2-hydroxybenzyl)amino)ethyl)amine)) have been prepared and their reactivity explored. The majority of the compounds are of formula Saltren(MR₂)₃ where M = B; R = OMe (1),

Full text of DOI:10.1016/S0022-328X(98)00544-0

Journal of Organometallic Chemistry 563 (1998) 87–93
Syntheses and reactions of Saltren–Group 13 complexes
Pingrong Wei, David A. Atwood *
Center for Main Group Chemistry, Department of Chemistry, North Dakota State Uni6ersity, Fargo, ND 58105-5516, USA
Received 9 January 1998
Abstract
Neutral Group 13 combinations with the Saltren ligand (tris(((2-hydroxybenzyl)amino)ethyl)amine)) have been prepared and
their reactivity explored. The majority of the compounds are of formula Saltren(MR2)3 where M=B; R=OMe (1), OEt (2), OnPr
i
(3); M=Al; R=Me (4), Et (5), Bu (6) and R=Et for M=Ga (7) and In (8). Mono-, [SaltrenHAlMe]n (9), and tetra-metallic,
Saltren(AlMe2)3–AlMe3 form when one and four equivalents of AlMe3 are added to the ligand. Compound 9 can be converted
to 4 by the addition of two or three additional molecules of AlMe3. Compounds 1 and 4 form unique zwitterionic compounds,
[SaltrenH3{M(OSiPh3)3}3] (M=B (11) and Al (12) when combined with six equivalents of Ph3SiOH. Attempts to prepare those
of formula Saltren{MR(OSiPh3)}3 where M=B and Al led to an inseparable mixture of compounds. All of the compounds were
characterized by standard techniques and, in the case of 1, 4, 7 and 12, by X-ray crystallography. © 1998 Elsevier Science S.A.
All rights reserved.
Keywords: Saltren; Group 13; Reactivity
1. Introduction
other multidentate ligands, such as the SaltrenH3(tris-
(((2-hydroxybenzyl)amino)ethyl)amine)) class. The use
of these and related ligands in the preparation of
charged Group 13 complexes, generally with a 1:1
metal–ligand stoichiometry, has already been demon-
strated [11]. The present study is focused on the prepa-
ration of neutral combinations between the SaltrenH3
ligand and the Group 13 elements.
The SalenH2(N,N%alkylene (or arylene) bis(salicyli-
deneimine)) ligands have been used extensively to sup-
port various Group 13 bonding schemes. Depending on
the metal, ligand, and stoichiometry, a diverse range of
structural types can be isolated. Predominant among
these are complexes having a 1:1 metal–ligand stoi-
chiometry {e.g. SalenMR (R=alkyl [1,2], halide or
amide [3], alkoxide [4], siloxide [2] and [SalenM(-
base)2]+ [5]} and those having a 2:1 metal–ligand
stoichiometry (e.g. Salen(MR2)2) {where M=B (R=
aryl [6] or alkoxide [7]), Al [8], Ga [9], In [10] (R=
alkyl)}. It would be interesting to discover whether the
same types of compounds might be accessible with
* Corresponding author. E-mail: Datwood@plains.nodak.edu
Scheme 1. General syntheses of compounds 1–10.
0022-328X/98/$19.00 © 1998 Elsevier Science S.A. All rights reserved.
PII S0022-328X(98)00544-0

88
P. Wei, D.A. Atwood / Journal of Organometallic Chemistry 563 (1998) 87–93
Fig. 2. Molecular structure and atom numbering scheme for
Saltren{AlMe2}3 (4).
1H-NMR displays two sharp singlets for the Al–Me
groups (AlMe2, −0.72, AlMe3, −0.92 ppm).
Fig. 1. Molecular structure and atom numbering scheme for
Saltren{B(OMe)2}3 (1).
When one equivalent of AlMe3 is combined with the
SaltrenH3 ligand a white solid precipitates (Scheme 1d).
An elemental analysis corresponds to the formula
[SaltrenHAlMe]n (9) which is presumably polymeric.
Similar products, for instance, are obtained when
AlMe3 is combined with ethylenediamine [13].
Combining 9 with 2 mol of AlMe3, either at ambient
temperature or with reflux in toluene, leads to high
yields of 4. It is notable that a molecule of formula
[SaltrenAlMe(AlMe2)]n is not isolated. This may indi-
cate that the Saltren ligand is not suitable for the
formation of aggregated compounds. Indeed, all of the
previously reported compounds have been monomeric
(with either one or two ligands around a central metal)
[11].
2. Results and discussion
2.1. Saltren–Group 13 alkyls
A homologous series of bimetallic Saltren derivatives
can be prepared by combining the Group 13 reagent
with the ligand in toluene. In order to obtain the boron
derivatives an alcohol elimination reaction must be
utilized since an alkane elimination route with BR3 is
not effectual (Scheme 1). The alcohol elimination has
been used previously to prepare boron derivatives of
various aminophenols [12] and Salen [7]. Alkane elimi-
nation reactions are, however, useful for the Al, Ga and
In derivatives (Scheme 1b). The spectroscopic data for
1–8 are consistent with the maintenance of a single
environment for the MR2 units. There is one resonance
for these groups and only one resonance for the imine
CH group. Thus, the ‘arms’ of the ligand are equivalent
in solution.
2.2. Saltren–Group 13 siloxides
There are relatively few molecular borosiloxanes and
aluminosiloxanes despite the fact that aluminosilicates
are one of the most prevalent materials on the earth.
This is due principally to the fact that the M–O–Si unit
tends to oligomerize. This tendency can be overcome by
the use of sterically encumbered ligands (such as the use
of 2,6-(iPr)2C6H5N(SiMe3)Si(OH)3 in the formation of
mineral-like aluminosilicates [14]) and often in conjunc-
tion with chelating ligands. This has been demonstrated
with acac (Al(OSiPh3)2(acac) (13) [15]) and salen lig-
ands (SalenAlOSiPh3 (14) [2]). In these compounds and
elsewhere, the Ph3SiO ligand has been of particular
utility {see, for instance, [(Ph3SiO)2Al(v-OtBu)]2 (15)
[16]}.
Compounds 1, 4 and 7 were characterized by X-ray
crystallography. Thus, a comparison can be made in
the behavior of the Saltren ligand through the series B,
Al and Ga (Figs. 1–3, respectively). Compounds 1 and
4 display structures that have approximate C3 symme-
try (space group R3 for 4). In this arrangement, the
MR2 groups are directed away from the center of the
molecule minimizing any contacts of these groups with
the ligand. In contrast, the gallium derivative appears
more randomly oriented with two of the GaEt2 groups
facing one another. The M–O(ligand) (1.487(5),
˚
1.724(7) and 1.875(8) A) and M–N distances (1.619(5),
˚
1.960(7), 2.025(7) A) increase through the series BB
AlBGa in keeping with the increasing size of the
atoms. Overall, these distances compare closely with
those of the related bimetallic Salen derivatives of
formula, Salen(MR2)2.
In each of the structures, the central nitrogen of the
ligand is arranged so that the lone electron pair is
pointed inward. However, it can still be used to coordi-
nate an external molecule of AlMe3 to form a te-
trametallic derivative (Scheme 1c). This is demonstrated
by addition of AlMe3 to 4 in the formation of 10. The
Fig. 3. Molecular structure and atom numbering scheme for
Saltren{GaEt2}3 (7).

P. Wei, D.A. Atwood / Journal of Organometallic Chemistry 563 (1998) 87–93
89
Fig. 5. General depiction of compounds 1–10 (a) and 11 and 12 (b).
3. Experimental section
Fig. 4. Molecular structure and atom numbering scheme for
SaltrenH3{Al(OSiPh3)3}3 (12).
3.1. General considerations
Thus, triphenylsilanol was viewed as a good ligand
for making Saltren–Group 13 siloxides. Accordingly,
the combination of six equivalents of the silanol with 1
and 4 was conducted with the expectation that the
compounds, Saltren{M(OSiPh3)2}3 might form. Sur-
prisingly, the isolated products are the Lewis acid–base
complexes SaltrenH3{M(OSiPh3)3}3 [with M=B (11)
and Al (12)]. The molecular structure of 12 is shown in
Fig. 4. The formation of 11 and 12 cannot be explained
by considering only the steric requirements of the
Ph3SiO ligand (Scheme 2). In compound 1, for exam-
ple, the chelate angle, O–Al–N is 94.4(3)° and the
Me–Al–Me% angle 116.0(3)°. In 13 these two angles are
115° (between the Ph3SiO groups) and 98° (the ‘bite’
angle of the acac ligand). Thus, it would appear that
two of the Ph3SiO groups could easily fit around an
aluminum atom having two of its coordination sites
taken up by the Saltren ligand. A general depiction of
compounds 1–12 is shown in Fig. 5 .
All manipulations were conducted using Schlenk
techniques in conjunction to an inert atmosphere glove
box. All solvents were rigorously dried prior to use.
NMR data were obtained on JEOL-GSX-400 and -270
instruments at 270.17 (1H) MHz. Chemical shifts are
reported relative to SiMe4 and are in ppm. Elemental
analyses were obtained on a Perkin-Elmer 2400 Ana-
lyzer. IR data were recorded as KBr pellets on a
Matheson Instruments 2020 Galaxy Series spectrometer
and are reported in cm−1 (see Section 4). The
SaltrenH3 ligand was prepared according to the litera-
ture [11]. X-ray data were collected on a Siemens CCD
diffractometer using graphite monochromated Mo–Kh
˚
(0.71073 A) radiation. All calculations were performed
on PC using the Siemens software package,
a
SHELXTL-Plus. Selected bond lengths and angles for
complexes 1, 4, 7 and 12 are listed in Table 1, while
details of the crystal data and a summary of data
collection parameters for the complexes are given in
Table 2.
The Al–O distances in 12 range from 1.694(11) to
˚
1.800(11) A. Those to the Saltren ligand are consis-
tently shorter than those to the Ph3SiO ligands. These
latter distances compare closely with those observed for
the (Ph3SiO)3Al–base {base=THF (16) [17], H2O (17)
[18] and Et2O (18) [18]} series of compounds. The
Al–O–Si angles for 12 as well as the majority of the
compounds reported in the literature span a fairly wide
range. For instance, in 12 they are 153.8(7) to 170.9(8)°
and in 15 they are 153.5(2) and 177.6(2)°.
The tris mono-siloxy derivatives Saltren{MR(OSi-
Ph3)}3 (M=B; R=OMe and M=Al, R=Me) could
not be prepared by the addition of three equivalents of
HOSiPh3 to 1 or 4. When these reactions are conducted
a mixture of products results.
3.2. Saltren[B(OMe)2]3 (1)
To a stirred toluene solution (25 ml) of SaltrenH3
(1.00 g, 2.15 mmol) was added trimethylborate (0.67 g,
6.46 mmol). The resulting solution was refluxed for 6 h.
After filtration and concentration, pale yellow crystals
were grown at −30°C (0.85 g, 61%). M.p. 184°C.
1H-NMR (270 MHz, CDCl3): l 2.91 (br, 6H, NCH2),
3.29 (s, 18H, OCH3), 3.81 (br, 6H, NCH2), 5.50 (d, 3H,
PhH), 6.32 (t, 3H, PhH), 7.03 (d, 3H, PhH), 7.43 (t,
3H, PhH), 8.59 (s, 3H, NCH). Analysis for
C33H45N4O9B3: Calc.: C 58.82, H 6.67. Found: C 59.14,
H 7.07%.
3.3. Saltren[B(OEt)2]3 (2)
The same procedure for 1 was followed with
SaltrenH3 (1.00 g, 2.15 mmol) and triethylborate (0.94
g, 6.46 mmol): yellow solid (1.0 g, 63%). M.p. 113°C.
Scheme 2. General synthesis of compounds 11 and 12.

90
P. Wei, D.A. Atwood / Journal of Organometallic Chemistry 563 (1998) 87–93
Table 1
˚
Selected bond lengths (A) and angles (°) for 1, 4, 7 and 12
Saltren{B(OMe)2}3 (1)
B(1)–O(3)
B(1)–O(2)
B(1)–O(1)
B(1)–N(1)
B(2)–O(6)
B(2)–O(5)
B(2)–O(4)
B(2)–N(2)
B(3)–O(8)
B(3)–O(9)
B(3)–O(7)
B(3)–N(3)
1.404(5)
1.422(5)
1.487(5)
1.619(5)
1.413(5)
1.418(5)
1.489(5)
1.588(5)
1.408(5)
1.412(5)
1.456(5)
1.616(5)
O(3)–B(1)–O(2)
O(3)–B(1)–O(1)
O(2)–B(1)–O(1)
O(3)–B(1)–N(1)
O(2)–B(1)–N(1)
O(1)–B(1)–N(1)
O(6)–B(2)–O(5)
O(6)–B(2)–O(4)
O(5)–B(2)–O(4)
112.4(3)
110.6(3)
112.5(3)
110.8(3)
104.3(3)
105.9(3)
113.4(4)
108.5(3)
110.6(3)
O(6)–B(2)–N(2)
O(5)–B(2)–N(2)
O(4)–B(2)–N(2)
O(8)–B(3)–O(9)
O(8)–B(3)–O(7)
O(9)–B(3)–O(7)
O(8)–B(3)–N(3)
O(9)–B(3)–N(3)
O(7)–B(3)–N(3)
110.4(3)
105.7(3)
108.1(3)
110.7(3)
111.3(4)
110.8(3)
106.2(3)
109.8(3)
107.9(3)
Saltren{AlMe2}3 (4)
Al(1)–O(1)
Al(1)–C(1)
Al(1)–C(2)
Al(1)–N(2)
1.724(7)
1.944(8)
1.948(7)
1.960(7)
1.306(9)
O(1)–Al(1)–C(1)
O(1)–Al(1)–C(2)
C(1)–Al(1)–C(2)
O(1)–Al(1)–N(2)
C(1)–Al(1)–N(2)
114.4(3)
111.4(3)
116.0(3)
94.4(3)
C(2)–Al(1)–N(2)
C(3)–O(1)–Al(1)
C(9)–N(2)–Al(1)
C(10)–N(2)–Al(1)
111.5(3)
132.5(7)
121.0(5)
120.7(6)
O(1)–C(3)
107.0(3)
Saltren{GaEt2}3 (7)
Ga(1)–O(1)
Ga(1)–C(28)
Ga(1)–C(30)
Ga(1)–N(1)
Ga(2)–O(2)
Ga(2)–C(34)
Ga(2)–C(32)
Ga(2)–N(2)
Ga(3)–C(38)
Ga(3)–O(3)
Ga(3)–N(3)
Ga(3)–C(36)
1.875(8)
1.926(11)
1.970(11)
2.025(7)
1.863(8)
1.92(2)
1.958(12)
1.994(10)
1.52(3)
O(1)–Ga(1)–C(28)
O(1)–Ga(1)–C(30)
C(28)–Ga(1)–C(30)
O(1)–Ga(1)–N(1)
C(28)–Ga(1)–N(1)
C(30)–Ga(1)–N(1)
O(2)–Ga(2)–C(34)
O(2)–Ga(2)–C(32)
C(34)–Ga(2)–C(32)
109.8(4)
108.0(5)
124.1(6)
92.6(4)
107.1(4)
110.7(4)
111.2(6)
108.7(5)
122.9(6)
O(2)–Ga(2)–N(2)
C(34)–Ga(2)–N(2)
C(32)–Ga(2)–N(2)
C(38)–Ga(3)–O(3)
C(38)–Ga(3)–N(3)
O(3)–Ga(3)–N(3)
C(38)–Ga(3)–C(36)
O(3)–Ga(3)–C(36)
N(3)–Ga(3)–C(36)
93.0(4)
112.5(7)
104.3(6)
107.2(7)
105.5(10)
92.9(4)
130.3(10)
105.9(6)
108.7(6)
1.875(9)
2.007(9)
2.02(2)
SaltrenH3{Al(OSiPh3)3}3 (12)
1.700(11)
Al(1)–O(6)
Al(1)–O(5)
Al(1)–O(4)
Al(1)–O(1)
Al(2)–O(8)
Al(2)–O(9)
Al(2)–O(7)
Al(2)–O(2)
Al(3)–O(11)
Al(3)–O(12)
Al(3)–O(10)
Al(3)–O(3)
Si(1)–O(4)
Si(2)–O(5)
Si(3)–O(6)
Si(4)–O(7)
Si(5)–O(8)
Si(6)–O(9)
Si(7)–O(10)
Si(8)–O(11)
Si(9)–O(12)
O(6)–Al(1)–O(5)
O(6)–Al(1)–O(4)
O(5)–Al(1)–O(4)
O(6)–Al(1)–O(1)
O(5)–Al(1)–O(1)
O(4)–Al(1)–O(1)
O(8)–Al(2)–O(9)
O(8)–Al(2)–O(7)
O(9)–Al(2)–O(7)
O(8)–Al(2)–O(2)
O(9)–Al(2)–O(2)
O(7)–Al(2)–O(2)
O(11)–Al(3)–O(12)
O(11)–Al(3)–O(10)
113.0(6)
114.9(5)
112.1(5)
108.4(5)
108.6(5)
98.6(5)
113.3(6)
114.3(5)
112.9(5)
108.2(5)
107.4(6)
99.5(5)
O(12)–Al(3)–O(10)
O(11)–Al(3)–O(3)
O(12)–Al(3)–O(3)
O(10)–Al(3)–O(3)
Si(1)–O(4)–Al(1)
Si(2)–O(5)–Al(1)
Si(3)–O(6)–Al(1)
Si(4)–O(7)–Al(2)
Si(5)–O(8)–Al(2)
Si(6)–O(9)–Al(2)
Si(7)–O(10)–Al(3)
Si(8)–O(11)–Al(3)
Si(9)–O(12)–Al(3)
112.8(5)
108.1(5)
106.7(5)
100.1(5)
153.8(7)
165.6(7)
169.3(7)
154.7(6)
173.6(7)
170.9(8)
159.7(7)
167.4(7)
168.0(7)
1.694(11)
1.719(10)
1.794(10)
1.688(10)
1.696(11)
1.716(10)
1.790(11)
1.701(10)
1.696(10)
1.718(10)
1.800(11)
1.611(10)
1.604(11)
1.604(11)
1.598(10)
1.597(11)
1.594(11)
1.600(10)
1.601(10)
1.603(10)
112.7(5)
115.2(5)
1H-NMR (270 MHz, CDCl3):
l
1.15 (m, 18H,
3.4. Saltren[B(OnPr)2]3 (3)
OCH2CH3), 2.95 (br, 6H, NCH2), 3.56 (m, 12H,
OCH2), 3.86 (br, 6H, NCH2), 5.49 (d, 3H, PhH), 6.30
(t, 3H, PhH), 7.00 (d, 3H, PhH), 7.42 (t, 3H, PhH),
8.66 (s, 3H, NCH). Analysis for C39H57N4O9B3: Calc.:
C 61.81, H 7.52. Found: C 61.81, H 7.74%.
The same procedure for 1 was followed with
SaltrenH3 (1.00 g, 2.15 mmol) and tri-n-propylborate
(1.22 g, 6.46 mmol): yellow solid (0.88 g, 49%). M.p.
1
45°C. H-NMR (270 MHz, CDCl3): l 0.85 (m, 18H,

P. Wei, D.A. Atwood / Journal of Organometallic Chemistry 563 (1998) 87–93
91
Table 2
Summary of data collection and structure solution parameters
Compound
(1)
(4)
(7)
(12)
Formula
C33H45B3N4O9
674.16
Monoclinic
P21/c
16.595(1)
11.6424(7)
18.708(1)
90
91.458(1)
90
C11H15AlN1.33
208.89
Trigonal
R−3
14.446(1)
14.446(1)
35.016(5)
90
90
120
6329(1)
18
O
C39H57Ga3N4O3
839.05
Triclinic
P−1
10.1989(7)
14.482(1)
16.368(1)
70.472(1)
79.414(1)
69.825(1)
2132.3(3)
2
C204H178Al3N4O12Si9
3353.05
Triclinic
Formula weight
Crystal system
Space group
P−1
˚
a (A)
19.796(1)
21.339(1)
25.486(1)
102.011(1)
97.891(1)
116.111(1)
9127.6(9)
2
˚
b (A)
˚
c (A)
h (°)
i (°)
k (°)
3
˚
V (A )
3613.4(4)
4
Z
F(000)
1432
1.239
0.2×0.4×0.7
Pale yellow, needle
298
2004
0.987
0.4×0.4×0.4
Pale yellow, cube
298
872
1.307
0.3×0.3×0.3
Pale yellow, cube
298
3518
1.220
0.4×0.4×0.4
Pale yellow, cube
298
Dcalc. (g cm−3
)
Crystal size (mm3)
Colour, habit
Temperature (K)
Absorption coefficient (mm−1
)
0.088
0.120
0.919
0.200
q range for data collection (°)
Reflections collected
Independent reflections
Data/restraints/parameters
R1
1.23–22.50
13267
4661 (Rint=0.0551)
7634/0/442
0.0659
1.73–16.47
4045
762 (Rint=0.0457)
707/0/130
0.0687
1.32–17.50
4846
2671 (Rint=0.0752)
2655/0/442
0.0550
1.11–19.00
24252
14150 (Rint=0.0381)
14083/0/2078
0.0755
Rall
0.0922
0.994
0.140, −0.168
0.1247
1.069
0.444, −0.413
0.0617
1.027
0.313, −0.685
0.0944
1.049
0.692, −0.438
Goodness-of-fit on F2
Largest difference peak and hole
CH2CH3), 1.50 (m, 12H, OCH2CH2), 2.93 (br. 6H,
NCH2), 3.45 (m, 12H, OCH2), 3.83 (br, 6H, NCH2),
5.53 (d, 3H, PhH), 6.26 (m, 3H, PhH), 6.90 (d, 3H,
PhH), 7.39 (m, 3H, PhH), 8.52 (s, 3H, NCH). Analysis
for C45H69N4O9B3: Calc.: C 64.20, H 8.19. Found: C
63.83, H 8.46%.
yellow solution and then filtered. The volatiles were
removed under reduced pressure. Recrystallization
from a hexane/toluene (5:1) yielded Saltren[Me2Al]3 (4)
(0.60 g) as determined by H-NMR.
3.6. Saltren[AlEt2]3 (5)
1
Prepared as for 4 with triethylaluminum (0.74 g, 6.46
mmol), toluene (20 ml) and SaltrenH3 (1.00 g, 2.15
mmol) in toluene (20 ml) yielding a yellow solid (1.4 g,
91%). M.p. 75°C. 1H-NMR (270 MHz, CDCl3): l
−0.08 (m, 12H, AlCH2), 0.96 (m, 18H, AlCH2CH3),
2.94 (br, 6H, NCH2), 3.57 (br, 6H, NCH2), 6.72 (m,
9H, PhH) 6.89 (m, 3H, PhH), 8.01 (s, 3H, NCH).
Analysis for C39H57N4O3Al3: Calc.: C 65.94, H 8.02.
Found: C 65.67, H 7.95%.
3.5. Saltren[AlMe2]3 (4)
Trimethylaluminum (0.47 g, 6.46 mmol) in 20 ml of
toluene was added to a rapidly stirred solution of
SaltrenH3 (1.00 g, 2.15 mmol) in toluene (20 ml) at
25°C. The vigorous exothermic reaction was allowed to
stir for 5 h, and the volatiles removed under reduced
pressure. Recrystallization from a hexane/toluene (5:1)
solution yielded yellow crystals suitable for single-crys-
1
tal X-ray analysis (1.30 g, 96%). M.p. 90°C. H-NMR
3.7. Saltren[Al(iBu)2]3 (6)
(270 MHz, CDCl3): 0 −0.74 (s, 18H, AlCH3), 2.89 (t,
6H, NCH2), 3.57 (t, 6H, NCH2), 6.65 (t, 3H, PhH),
6.78 (d, 3H, PhH), 6.85 (d, 3H, PhH), 7.41 (t, 3H,
PhH), 7.89 (s, 3H, NCH). Analysis for C33H45N4O3Al3:
Calc.: C 63.28, H 7.18. Found: C 63.15, H 7.04%.
Prepared as for 4 with tri-iso-butylaluminum (1.28 g,
6.46 mmol) in toluene (20 ml) and SaltrenH3 (1.00 g,
2.15 mmol) in toluene (20 ml) to yield a yellow solid
1
(1.1 g, 58%). M.p. 60°C. H-NMR (270 MHz, CDCl3):
l −0.01 (m, 12H, AlCH2), 0.90 (m, 36H, CH(CH3)2),
1.80 (m, 6H, CH2CH), 2.92 (t, 6H, NCH2), 3.55 (t, 6H,
NCH2), 6.72 (t, 3H, PhH), 6.87 (d, 3H, PhH), 7.00 (d,
3H, PhH), 7.41 (t, 3H, PhH), 7.98 (s, 3H, NCH).
Analysis for C51H81N4O3Al3: Calc.: C 69.72, H 9.22.
Found: C 69.58, H 9.11%.
3.5.1. Alternate synthesis of 4
Trimethylaluminum (0.18 g, 2.50 mmol) in toluene
(20 ml) was added to a rapidly stirred suspension of 9
(0.65 g, 1.25 mmol) in toluene (30 ml) at 25°C. The
mixture was stirred at reflux for 3 h, resulting in a clear

92
P. Wei, D.A. Atwood / Journal of Organometallic Chemistry 563 (1998) 87–93
3.8. Saltren[GaEt2]3 (7)
(1.70 g, 6.18 mmol). The resulting solution was refluxed
for 5 h. Removal of solvent under vacuum followed by
recrystalization from CH2Cl2 solution yielded a yellow
solid (1.4 g, 47%). M.p. 144°C. H-NMR (270 MHz,
CDCl3): l 2.60 (m, 6H, NCH2), 3.05 (m, 6H, NCH2),
5.75 (m, 3H, PhH), 6.33 (m, 3H, PhH), 6.48 (m, 3H,
PhH), 7.07–7.42 (br, 138H, PhH), 7.57 (m, 3H, NCH).
Analysis for C189H165N4O12Si9B3: Calc.: C 76.57, H
5.56. Found: C 76.23, H 5.40%.
Prepared as for 4 with triethylgallium (1.35 g, 8.62
mmol) in toluene (20 rnL) and SaltrenH3 (1.00 g, 2.15
mmol) in toluene (20 ml) to yield yellow crystals (1.1 g,
1
1
61%). M.p. 83°C. H-NMR (270 MHz, CDCl3): l 0.41
(m, 12H, GaCH2), 1.03 (m, 18H, CH2CH3), 2.85 (t, 6H,
NCH2), 3.63 (t, 6H, NCH2), 6.59 (m, 3H, PhH), 6.84
(m, 6H, PhH), 7.75 (m, 3H, PhH), 7.85 (s, 3H, NCH).
Analysis for C39H57N4O3Ga3: Calc.: C 55.85, H 6.79.
Found: C 55.97, H 6.56%.
3.13. SaltrenH3[Al(OSiPh3)3]3 (12)
3.9. Saltren[InEt2]3 (8)
Prepared as for 11 with Saltren[AlMe2]3 (0.63 g, 1.00
mmol) in toluene (30 ml) and triphenylsilanol (1.66 g,
6.00 mmol) to yield orange crystals at −30°C (1.3 g,
44%). M.p. 173°C. 1H-NMR (270 MHz, CDCl3): l 0.93
(m, 6H, NCH2), 2.20 (m, 6H, NCH2), 5.02 (m, 3H,
PhH), 5.88 (m, 3H, PhH), 6.73–7.51 (br, 141H, PhH),
Prepared as for 4 with triethylindium (1.31 g, 6.46
mmol) in toluene (20 ml) and SaltrenH3 (1.00 g, 2.15
mmol) in toluene (20 ml) to yield a yellow solid, (1.9 g
91%). M.p. 187°C. 1H-NMR (270 MHz, DMSO): l
0.45 (m, 12H, InCH2), 1.10 (m, 18H, CH2CH3), 2.85
(br, 6H, NCH2), 3.60 (br, 6H, NCH2), 6.45 (t, 3H,
PhH), 6.61 (d, 3H, PhH), 7.15 (m, 6H, PhH), 8.22 (s,
3H, NCH). Analysis for C39H57N4O3In3: Calc.: C
48.09, H 5.85. Found: C 48.03, H 5.44%.
11.70
(m,
3H,
NCH).
Analysis
for
C189H165N4O12Si9Al3: Calc.: C 75.33, H 5.47. Found: C
75.14, H 5.28%.
4. Supplementary material available
3.10. [SaltrenH(AlMe)]n (9)
Tables of atomic coordinates and equivalent
isotropic thermal parameters, hydrogen atom parame-
ters, anisotropic thermal parameters and bond lengths
and angles for 1, 4, 7 and 12 are available on request
from the authors.
Trimethylaluminum (0.23 g, 3.23 mmol) in 20 ml of
toluene was added to a rapidly stirred solution of
SaltrenH3 (1.50 g, 3.23 mmol) in toluene (20 ml) at
25°C. The addition took place over 3–5 min, resulting
in a yellow solution and pale yellow solid. The mixture
was allowed to stir for 5 h at 25°C, and then filtered.
The solid was dried in vacuo, yielding 1.0 g, 93%.
M.p.\260°C. Analysis for C28H31N4O3Al: Calc.: C
67.42, H 6.22. Found: C 66.99, H 5.92%.
Acknowledgements
Gratitude is expressed to the National Science Foun-
dation (Grant 9452892) and the donors of the
Petroleum Research Fund (Grant 31901-AC3), admin-
istered by the American Chemical Society, for support.
The receipt of an NSF-CAREER award (CHE-
9625376) is also gratefully acknowledged.
3.11. Saltren[AlMe2]3[AlMe3] (10)
Trimethylaluminum (0.62 g, 8.62 mmol) in 20 ml of
toluene was added to a rapidly stirred solution of
SaltrenH3 (1.00 g, 2.15 mmol) in toluene (20 ml) at 25
C. The vigorous exothermic reaction was allowed to
–
stir for 5 h, and the volatiles removed under reduced
pressure. Recrystallization from a hexane/toluene (5:1)
solution yielded a yellow solid (1.2 g, 80%). M.p. 80°C.
1H-NMR (270 MHz, CDCl3): l −0.92 (s, 9H, AlCH3),
−0.72 (s, 18H, AlCH3), 2.94 (t, 6H, NCH2), 3.62 (t,
6H, NCH2), 6.82 (t, 3H, PhH), 6.96 (m, 6H, PhH), 7.44
(t, 3H, PhH), 8.00 (s, 3H, NCH). Analysis for
C36H54N4O3Al4: Calc.: C 61.91, H 7.73. Found: C
61.52, H 7.47%.
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