Aryl(silyl)amino group stabilized hydridosilanediols: Synthesis and characterization and use for preparation of alumino(hydrido)siloxanes

Article abstract of DOI:10.1039/c6dt00059b

Aryl(silyl)amino group stabilized hydridosilanediols RSiH(OH)₂ (R = N(SiMe₂Ph)-2,6-iPr₂C₆H₃ (4), N(SiMe₃)-2,6-iPr₂C₆H₃ (5), and N(SiMe₂Ph)-2,4,6-Me₃C₆H₂ (6)) were prepared from the controlled hydrolysis of the related RSiHCl₂ (1-3) each in the presence of aniline as the HCl acceptor. Reactions of 4 with AlMe₃, AliBu₃, AlH(iBu)₂, and AlH₃·NMe₃, respectively, yielded alumino(hydrido)siloxanes [2,6-iPr₂C₆H₃N(SiMe₂Ph)Si(H)OAlMe(THF)]₂ (7), [2,6-iPr₂C₆H₃N(SiMe₂Ph)Si(H)OAliBu(THF)]₂ (9), [2,6-iPr₂C₆H₃N(SiMe₂Ph)Si(H)O₂]₃[Al(THF)]₂ (10), and [2,6-iPr₂C₆H₃N(SiMe₂Ph)Si(H)OAlH(THF)]₂ (11). The reaction of 5 with AlMe₃ gave [2,6-iPr₂C₆H₃N(SiMe₃)Si(H)OAlMe(THF)]₂ (8), a compound similar to 7. Compounds 1-11 are characterized by NMR (¹H, ¹³C, and ²⁹Si) and IR spectroscopy and CHN elemental analysis, of which 6 and 8-11 are further studied by X-ray crystallography. Compounds 8-9 and 11 feature cyclic structures all with the skeleton core of Si₂O₄Al₂ while compound 10 exhibits a bicyclic structure having a core of Si₃O₆Al₂. Melting point measurements indicated that 4-6 are thermally stable bearing the geminal SiH and SiOH groups. Compounds 8-9 and 11 are thermally stable as well with the O atom-bridged SiH and AlR (R = Me, iBu, or H) groups.

Full text of DOI:10.1039/c6dt00059b

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Aryl(silyl)amino group stabilized hydridosilanediols:
synthesis and characterization and use for
preparation of alumino(hydrido)siloxanes†
Cite this: DOI: 10.1039/c6dt00059b
Xiaoping Wang,a Jiancheng Li,a Shimin Chen,a Weiping Liu,b Qingsong Yeb and
Hongping Zhu*a
Aryl(silyl)amino group stabilized hydridosilanediols RSiH(OH)2 (R = N(SiMe2Ph)-2,6-iPr2C6H3 (4), N(SiMe3)-
2,6-iPr2C6H3 (5), and N(SiMe2Ph)-2,4,6-Me3C6H2 (6)) were prepared from the controlled hydrolysis of the
related RSiHCl2 (1–3) each in the presence of aniline as the HCl acceptor. Reactions of 4 with AlMe3,
AliBu3, AlH(iBu)2, and AlH3·NMe3, respectively, yielded alumino(hydrido)siloxanes [2,6-iPr2C6H3N(SiMe2Ph)
Si(H)OAlMe(THF)]2 (7), [2,6-iPr2C6H3N(SiMe2Ph)Si(H)OAliBu(THF)]2 (9), [2,6-iPr2C6H3N(SiMe2Ph)Si(H)
O2]3[Al(THF)]2 (10), and [2,6-iPr2C6H3N(SiMe2Ph)Si(H)OAlH(THF)]2 (11). The reaction of 5 with AlMe3 gave
[2,6-iPr2C6H3N(SiMe3)Si(H)OAlMe(THF)]2 (8), a compound similar to 7. Compounds 1–11 are character-
ized by NMR (1H, 13C, and 29Si) and IR spectroscopy and CHN elemental analysis, of which 6 and 8–11 are
further studied by X-ray crystallography. Compounds 8–9 and 11 feature cyclic structures all with the
skeleton core of Si2O4Al2 while compound 10 exhibits a bicyclic structure having a core of Si3O6Al2.
Melting point measurements indicated that 4–6 are thermally stable bearing the geminal SiH and SiOH
groups. Compounds 8–9 and 11 are thermally stable as well with the O atom-bridged SiH and AlR (R =
Me, iBu, or H) groups.
Received 6th January 2016,
Accepted 1st March 2016
DOI: 10.1039/c6dt00059b
www.rsc.org/dalton
the corresponding silanediol and silanetriol through iodiza-
tion followed by hydrolysis.6 Compounds (Me2PhSi)3CSiMeH
Introduction
Organosilanols with the general formula of RnSi(OH)4−n (n = (OH),7 tBu2SiH(OH),8 and 2,6-Mes2C6H3SiH(OH)2 (Mes = 2,4,6-
1–3, R = organic group) are useful precursors, and have been Me3C6H2)9 have been prepared and characterized by X-ray
extensively utilized for the synthesis of metallasiloxanes and structural analysis. However, the use of these compounds for
Si-based organyl polymers.1,2 The metallasiloxanes are usually preparing the metallasiloxanes has not been reported so far.
considered to be important structural models for naturally Recently, periodic mesoporous hydridosilica (PMHS) was syn-
occurring metallasilicates, synthesized metal-containing zeo- thesized10 and further employed to transform Ag(I) into mole-
lites,3 and heterogeneous metal catalysts supported in silica.4 cularly scaled Ag(0) nanoclusters, in which the hydrido group
Some of the metallasiloxanes have been successfully employed functioned as a reducing group. These metal nanoclusters
as catalysts for homogeneously catalytic reactions.5 Among formed were located in the pore wall of the PMHS micro-
these organosilanols, the hydridosilanol is reported to a much sphere.11 We and others have more recently used RSiMe(OH)2
lesser extent.2 Species (Me3Si)3CSiPhH(OH) and (Me3Si)3CSi- and RSi(OH)3, where R is N(SiMe3)-2,6-iPr2C6H3, and prepared
H2(OH) have even been mentioned to mediate the synthesis of the metallasiloxanes of the group 13–15 heavier elements5d
and Cu metal.5c We were then motivated to approach species
RSiH(OH)2 as R had been proven to be a promising stabilizing
group.2 Complexes RSiH(OH)2 (R = N(SiMe2Ph)-2,6-iPr2C6H3
(4), N(SiMe3)-2,6-iPr2C6H3 (5), and N(SiMe2Ph)-2,4,6-Me3C6H2
(6)) were successfully prepared from controlled hydrolysis of
the related RSiHCl2 (1–3). Further reaction by using 4 with
coinage metal aryl compounds (MMes)n (M = Cu, Ag) resulted
in M(0) nanocrystals.12 Although this result is against that of
the formation of the Cu(I) siloxane through the RSi(OH)3
precursor,5c it evidences a remarkable reducing reactivity of
the SiH group in a similar manner to that of PMHS. In
contrast, the reactions of 4 (or 5) with organoaluminum
aState Key Laboratory of Physical Chemistry of Solid Surfaces, National Engineering
Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters, College of
Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.
E-mail: hpzhu@xmu.edu.cn
bState Key Laboratory for Platinum Group Metals, Kunming Institute of Precious
Metals, Kunming, Yunnan Province 650106, China
†Electronic supplementary information (ESI) available: Table of crystal data col-
lection and structure refinements and crystal structures of 6 and 11. Table of
selected bond parameters of 8–11. The NMR (1H, 13C, and 29Si) spectra of 1–11.
CCDC 1442616 (6), 1442617 (8), 1442618 (9), 1442619 (10) and 1442615 (11). For
ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/
c6dt00059b
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reagents led to the formation of stable alumino(hydrido)silo- versus δSiMe 12.2–12.5 ppm).16 In addition, the 1H NMR
3
xanes, a novel type of metallasiloxane that was characterized to spectra exhibit doublet (at δ 1.08 and 1.11 ppm for 1 and
have the hydrido group intact at the Si atom forming either 1.18 and 1.26 ppm for 2) and septet resonances (at δ 3.53 ppm
the Si2O4Al2 or Si3O6Al2 skeleton.
for 1 and 3.41 ppm for 2), which are characteristic of CHMe2
and CHMe2 of the aryl substituents. In the H NMR spectrum
1
of 3, the aryl o-Me and p-Me resonate at δ 2.45 and 2.47 ppm,
respectively, both as a singlet.
Results and discussion
Controlled hydrolysis of compounds 1–3 was conducted in
Et2O by using water of two equivalents, in which two equi-
valents of aniline was employed as the HCl acceptor. Following
the production of large amounts of salt PhNH2·HCl from 0 °C
to room temperature, target compounds RSiH(OH)2 (R =
N(SiMe2Ph)-2,6-iPr2C6H3 (4), N(SiMe3)-2,6-iPr2C6H3 (5), and
N(SiMe2Ph)-2,4,6-Me3C6H2 (6)) were hereupon formed
(Scheme 1). Compounds 4 and 5 were obtained each as an off-
white solid with the respective isolated yields of 95% and 87%.
Compound 6 was cropped as colorless crystals in 76% yield
(Scheme 1). These three compounds were measured to have
definite melting points (at 97 °C for 4, 116 °C for 5, and 43 °C
for 6). Subsequent 1H NMR spectra test of the samples after
the m.p. measurement showed no change of the data. These
results indicate that compounds 4–6 are thermally stable.
Compounds 4–6 are characterized by NMR (1H, 13C, and
29Si) and IR spectroscopy. Selected data for the SiH(OH)2
moiety of 4–6 are summarized in Table 1. The SiH resonates at
δ 4.55 ppm for 4, 4.69 ppm for 5, and 4.58 ppm for 6. These
data appear in a little higher resonance field when compared
with those of 1–3, and should account for the change of the
two Cl atoms by the two OH groups at the Si center. The IR
spectra display the corresponding vibration bands for the Si–H
bond around ˜ν 2200 cm−1. It should be noted that one new
Synthesis and characterization of aryl(silyl)amino group
stabilized hydridosilanediols
A one-pot reaction was employed to prepare the aryl(silyl)
amino group (R) stabilized hydrido(dichloro)silane RSiHCl2
(R = N(SiMe2Ph)-2,6-iPr2C6H3 (1), N(SiMe3)-2,6-iPr2C6H3 (2),
and N(SiMe2Ph)-2,4,6-Me3C6H2 (3)) when starting from
primary arylamine ArNH2 (Ar
= 2,6-iPr2C6H3 or 2,4,6-
Me3C6H2). In general, connection of the silyl group (SiR′3
=
SiMe2Ph or SiMe3) instead of the H atom at the N atom of the
arylamine was realized through nBuLi-lithiation of ArNH2,
followed by metallation reaction with ClSiR′3. Compound
ArNHSiR′3 formed was not isolated but used for further
reaction with nBuLi and subsequent metallation with SiHCl3.
Complexes 1–3 were obtained in yields of 65%, 62%, and 80%,
respectively. They were characterized by NMR (1H, 13C, and
29Si) and IR spectroscopy and CHN elemental analysis. In the
1H NMR spectra, proton resonances at δ 5.39 ppm for 1,
5.50 ppm for 2, and 5.80 ppm for 3 are assigned to SiH
(Table 1). These data are comparable to those of SiHCl3
(δH 6.09 ppm)13 and Mes2C6H3SiHCl2 (δH 4.94 ppm).14 More-
over, the IR spectra show typical stretching frequencies for the
Si–H bond (at ˜ν 2228 cm−1 for 1, 2254 cm−1 for 2, and
2223 cm−1 for 3).15 The 29Si NMR spectra each show two
silicon resonance signals; resonances at δSi −21.5 ppm for 1,
−22.0 ppm for 2, and −23.0 ppm for 3 are due to SiHCl2 while
those at δ 1.2 ppm for 1 and 1.6 ppm for 3 to the SiMe2Ph and
at δ 11.2 ppm for 2 to SiMe3. The former resonances are sig-
nificantly upfield mostly because of attachment of the chlorine
atoms at the Si nuclei. Similar data have been found in
compounds ArN(SiMe3)SiMeCl2 (Ar = 2,6-Me2C6H3, 2,6-iPr2C6H3,
2,4,6-Me3C6H2; δSiMeCl −1.2 to −1.3 ppm versus δSiMe
1
broad resonance is observed in each of the H NMR spectra of
these three compounds (δ 2.47 ppm for 4, 2.48 ppm for 5, and
2.39 ppm for 6, all recorded in CDCl3), which appears to be
independent of concentration and is therefore assignable to
the SiOH proton. Comparable resonance can be found in
[Fc2SiOH]2(μ-O) (Fc = C5H4FeC5H5, δSiOH 2.66 ppm in CDCl3)17
and Ph3SiOH (δSiOH 2.48 ppm in CDCl3).18 Furthermore, the IR
spectra show the stretching frequencies as sharp peaks
(˜ν 3550 cm−1 for 4, 3554 cm−1 for 5, and 3574 cm−1 for 6) for
the Si–O–H while as broad peaks (˜ν 3359 cm−1 for 4,
3319 cm−1 for 5, and 3280 cm−1 for 6) for the Si–O–H⋯O–Si,
respectively. The latter IR bands suggest the formation of the
hydrogen bond, which is able to be affirmed by the X-ray
2
3
10.3–10.4 ppm) and ArN(SiMe3)SiCl3 (δSiCl −27.9 to −28.3 ppm
3
Table 1 Summarized NMR and IR data for the SiHCl2 (1–3), SiH(OH)2
(4–6), and Si(H)OAl (7–11) moieties
NMR (δ, ppm, in CDCl3)
IR (˜ν, cm−1
)
Comp.
SiH
SiOH
SiH
Si–OH
Si–H
1
2
3
4
5
6
7
8
5.39
5.50
5.80
4.55
4.69
4.58
4.55
4.64
4.58
5.04
4.58
—
—
—
2.47
2.48
2.39
—
—
—
–21.5
–22.0
–23.0
–45.7
–46.4
–47.2
–66.2
–66.5
–65.1
–59.3
–65.7
—
—
—
2228
2254
2223
2200
2201
2198
2120
2107
2109
2134
2113
3550, 3359
3554, 3319
3574, 3280
—
—
—
—
—
9
10
11
—
—
Scheme 1 Controlled hydrolysis of compounds 1–3 to produce 4–6.
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crystal structural analysis of complex 6 (vide infra). Similar IR
data for the Si-based hydroxyls have been shown in 2,6-
Mes2C6H3SiH(OH)2.9 In periodic mesoporous hydridosilica
(meso-HSiO1.5), there is reported a sharp Si–H stretching
vibration at ca. ˜ν 2255 cm−1. A broad peak is also present at
ca. ˜ν 3500 cm−1, which is, however, proposed to be due to Si–
O–H⋯H–Si.19 Like the 29Si NMR data of 1–3, two silicon reson-
ances were observed as well for compounds 4–6; resonances at
δ −45.7 ppm for 4, −46.4 ppm for 5, and −47.2 ppm for 6
correspond to SiH and those at δ −1.9 ppm for 4 and −1.7 ppm
for 6 to SiMe2Ph and that at δ 7.1 ppm for 5 to SiMe3.
Scheme 2 Reactions of 4 and 5 each with AlMe3 to yield 7 and 8.
An X-ray diffraction study of 6 unambiguously confirms its
structure and composition in agreement with those disclosed
from the NMR and IR spectroscopy as well as the CHN elemen-
tal analysis. The crystal structure of 6 with selected bond
lengths and angles is shown in Fig. 1. The Si–O bond lengths
are within 1.625(2)–1.640(2) Å and the O–Si–O bond angles
within 102.8(9)–106.1(9)°. It has to be mentioned that the
intramolecular hydrogen bonding is clearly found in 6 to be
involved among the hydroxyl groups (SiO–H⋯O(H)Si 1.852(1)–
2.010(1) Å), and as a result a one-dimensional network struc-
ture is actually formed (see Fig. S1 in the ESI†).
failed. It appears that the use of the THF donor solvent seems
important for obtaining 7 as the product, because when using
n-hexane or toluene as the solvent, the reaction yielded a
mixture of products that was hard to separate into the pure
compound. As a matter of fact, in 7 THF is coordinated at the
Al center. We have tried to dissociate this THF donor by heat
treatment (over its melting point of 167 °C, vide infra) under
evacuation, but failed. Under similar conditions for synthesiz-
ing 7, compound [2,6-iPr2C6H3N(SiMe3)Si(H)OAlMe(THF)]2 (8)
was readily prepared from the reaction of 5 and AlMe3 in a
molar ratio of 2 : 2 in THF at room temperature (Scheme 2).
The reaction of 4 with AliBu3 in a molar ratio of 2 : 2 led in
THF at room temperature to compound [2,6-iPr2C6H3N
(SiMe2Ph) Si(H)OAliBu(THF)]2 (9), a similar product to 7 (or 8),
but via the elimination of isobutane. Further test by choosing
AlHiBu2 instead, however, yielded under the same conditions
[2,6-iPr2C6H3N(SiMe2Ph)Si(H)O2]3[Al(THF)]2 (10, Scheme 3), a
product different from 9, in which all the H and iBu base
groups of AlHiBu2 were reacted whether we used a molar ratio
of 2 : 2 or 3 : 2. This result suggests a better reactivity of
AlHiBu2 than that of AliBu3 (or AlMe3) in terms of a complete
reaction of the three base groups at the Al atom toward the
silanol protons of 4. The greater reactivity of the AlH than
the AliBu has been found in the reaction of RSi(OH)3
and AlHiBu2 to compounds [R(HO)SiO2AliBu(THF)]2 and
Reactions of aryl(silyl)amino group stabilized
hydridosilanediols with organoaluminum reagents
By selecting 4 as a reactant, the reaction with aluminum tri-
methyl was first carried out. These two compounds were set at
a molar ratio of 2 : 2 and they reacted smoothly in THF at room
temperature, affording compound [2,6-iPr2C6H3N(SiMe2Ph)Si
(H)OAlMe(THF)]2 (7) through elimination of four molecules of
methane (Scheme 2). In an attempt to promote a further reac-
tion of one methyl base group retained at the Al center of 7,
the reaction of these two compounds with a molar ratio of 3 : 2
was also carried out. However, compound 7 was still produced
under the same conditions and no new product was obtained.
Upon heat treatment (at 50 °C or even under reflux), a mixture
1
of products was formed, as indicated by the H NMR spectral
analysis of the residue obtained from the removal of all
volatiles after the reaction. Isolation of the pure new species
Fig. 1 X-ray crystal structure of 6 with thermal ellipsoids at the 50%
probability level. H atoms except for those of SiH and OH are omitted
for clarity. Selected bond lengths (Å) and angles (°) (the value in the
bracket is for another independent molecule): Si(1)–H(1) 1.40(2) [1.38(2)],
Si(1)–O(1) 1.625(2) [1.634(2)], Si(1)–O(2) 1.635(2) [1.640(2)]; O(1)–Si(1)–
O(2) 106.1(9) [102.8(9)].
Scheme 3 Reaction of
AlH3·NMe3 to yield 9–11.
4
with the respective AliBu3, AlHiBu2, and
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(RSiO3Al2iBu3)2 (R
=
N(SiMe3)-2,6-iPr2C6H3) in different 3.99 ppm, respectively, each as a broad peak as well. Further-
temperature ranges (from −78 °C to room temperature).20 more, the IR band at ˜ν 1841 cm−1 is due to a vibration of the
Then, the reaction of 4 with aluminum hydride AlH3·NMe3 Al–H bond, which appears red-shifted when compared with
was finally performed. By setting a molar ratio of 3 : 2 the reac- that of the Si–H bond.
tion underwent a smooth elimination of six molecules of H2 in
Compounds 8–11 are further characterized by X-ray crystallo-
THF at room temperature to produce 10, the same result as graphy. Compound 8 crystalizes into a triclinic crystal system
ˉ
that from the reaction of 4 and AlHiBu2. It was interesting to with space group P1 whereas compounds 9–11 crystalize into
find that, by controlling the temperature starting from −20 °C the monoclinic system with space groups of Cc, P2(1)/n, and P2
to room temperature, compound [2,6-iPr2C6H3N(SiMe2Ph)Si (1)/c, respectively. The crystal structures of 8–11 are depicted in
(H)OAlH(THF)]2 (11) was yielded from the reaction of 4 and Fig. 2–5 with selected bond lengths and angles. In general,
AlH3·NMe3, in the molar ratio of 2 : 2 with the elimination of compounds 8–9 and 11 adopt a cyclic structure all with a
four H2 molecules (Scheme 3).
Si2O4Al2 eight-membered ring core, and compound 10 features
Compounds 7–10 were isolated each as an off-white solid a bicyclic structure having a skeleton core of Si3O6Al2.
and compound 11 was cropped as colorless crystals, all in rela- Among the organosilanol-derived aluminosilxanes of the ring
tively good yields (66% for 7, 71% for 8, 62% for 9, 64% for 10, ([2,6-iPr2C6H3N(SiMe3)(Me)SiO2AlMe(THF)]2,5d [2,6-iPr2C6H3N-
and 68% for 11). They are all moisture-sensitive but stable (SiMe3)Si(OH)O2AliBu(THF)]2),20 and [L′Al(μ-O)(R2Si)(μ-O)]2 (R
under an inert atmosphere (Ar or N2). These compounds are
thermally stable. They have clear melting points (at 167 °C for
7, 196 °C for 8, 157 °C for 9, 147 °C for 10, and 135 °C for 11),
and the 1H NMR spectral test of the samples after the m.p.
measurement showed no change of the data. Compounds 7–11
are soluble in common organic solvents such as hydrocarbons
(n-C6H14, C6H6, and C7H8), chlorinated hydrocarbons (CHCl3
and CH2Cl2), and donor solvents (Et2O and THF). They have
been characterized by NMR (1H, 13C, and 29Si) and IR spectro-
scopy as well as by CHN elemental analysis.
In the 1H NMR spectra, these compounds exhibit SiH
proton resonance at δ 4.55 ppm for 7, 4.64 ppm for 8,
4.58 ppm for 9, 5.04 ppm for 10, and 4.58 ppm for 11, all close
to those of 1–6 (Table 1). Together with the IR bands for the
Si–H bond (˜ν 2120 cm−1 for 7, 2107 cm−1 for 8, 2109 cm−1 for
9, 2134 cm−1 for 10, and 2113 cm−1 for 11), these data are of
the typical character, in line with those of the hydrido silicon
Fig. 2 X-ray crystal structure of 8. H atoms except for those of SiH are
omitted for clarity. Selected bond lengths (Å) and angles (°): Si(1)–H(1)
1.44(2), Si(1)–O(1) 1.597(1), Si(1)–O(2) 1.598(2), Al(1)–O(1) 1.712(1), Al(1)–
compounds.15 In contrast, a significant change of the SiH
O(2A) 1.714(2), Al(1)–C(1) 1.941(3); O(1)–Si(1)–O(2) 113.3(8), O(1)–Al(1)–
resonances is observed (δ −66.2 ppm for 7, −66.5 ppm for 8,
O(2A) 115.7(8), Si(1)–O(1)–Al(1) 151.0(1), Si(1)–O(2)–Al(1A) 149.3(1). Sym-
−65.1 ppm for 9, −59.3 ppm for 10, and −65.7 ppm for 11, see
Table 1), which is mostly due to their formation into the Si
(H)–O–Al links, whereas the resonance shows little change
for the SiMe2Ph (δ −5.8 ppm for 7, −5.5 ppm for 9, −3.5 ppm
for 10, and −5.4 ppm for 11) and the SiMe3 (δ 2.5 ppm for 8).
The AlMe methyl in compounds 7 and 8 is indicated by the
proton resonances at δ −1.00 and −1.00 ppm as well as by the
carbon resonances at δ −14.0 and −14.1 ppm, respectively.
These data are typical and similar resonance values have been
metry code for A: −x, −y + 1, −z + 1.
shown in aluminosiloxanes [RSi(Me)OAlMe(THF)]2 (R
=
N(SiMe3)-2,6-iPr2C6H3, δH(AlMe) −1.06 and δC(AlMe) −14.4 ppm)
and (RSiO3)2[AlMe(THF)]3 (δH(AlMe) −1.03 and δC(AlMe)
−13.6 ppm).5d The resonances at δ −0.32, 1.71, and 0.83 ppm
are assignable to the AliBu isobutyl of the AlCH2CH(CH3)2,
AlCH2CH(CH3)2, and AlCH2CH(CH3)2, respectively, with satis-
Fig. 3 X-ray crystal structure of 9. H atoms except for those of SiH are
factory integration of 2 : 1 : 6, in the 1H NMR spectrum of 9 omitted for clarity. Selected bond lengths (Å) and angles (°): Si(1)–H(1)
recorded in D6-DMSO. Notably, in the 1H NMR spectrum of 11,
the AlH resonance was able to be observed at δ 3.31 ppm as a
1.43(3), Si(3)–H(3) 1.45(3), Si(1)–O(1) 1.631(8), Si(1)–O(2) 1.624(7), Si(3)–
O(3) 1.579(7), Si(3)–O(4) 1.572(8), Al(1)–O(1) 1.701(8), Al(1)–O(4) 1.769(8),
Al(2)–O(2) 1.668(8), Al(2)–O(3) 1.723(7), Al(1)–CiBu 2.013(12); O(1)–Si(1)–
O(2) 113.2(4), O(3)–Si(3)–O(4) 112.1(4), O(1)–Al(1)–O(4) 114.8(4), O(2)–
broad signal. In compound LAlH(NHAr) (L = HC[(CMe)
(N-2,6-iPr2C6H3)]2)21a and [{L′Al(H)}2(μ-O)] (L′ = HC[(CMe)
Al(2)–O(3) 114.6(4), Si(1)–O(1)–Al(1) 158.3(5), Si(1)–O(2)–Al(2) 147.6(5),
(N-2,4,6-Me3C6H2)]2),21b the AlH resonates at δ 5.50 ppm and Si(3)–O(3)–Al(2) 159.0(5), Si(3)–O(4)–Al(1) 145.9(5).
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centers are four-coordinate in a distorted tetrahedral geometry
(O–Al–O 112.0(1)–115.7(5)° and O–Si–O 111.9(1)–113.3(8)°, see
Table S2 in the ESI†) and the O atom is two-coordinate
presenting a bent geometry (Si–O–Al 128.9(2)–158.3(5)°, see
Table S2 in the ESI†). These structural features fall well within
the Loewenstein rule which states that an oxygen atom bridges
Si and Al tetrahedra, one of the fundamental principles used
to illustrate the complicated structure of aluminosilicates.22e,23
The Al–O bond lengths (1.668(8)–1.769(8) Å) are a little longer
than those of the Si–O bond lengths (1.572(7)–1.631(8) Å). The
Al–C bond lengths are 1.941(3) Å in 8 (Al–CMe) and 2.013(12) Å
in 9 (Al–CiBu), respectively.
Conclusions
In summary, aryl(silyl)amino group stabilized hydrido
(dichloro)silanes RSiHCl2 (1–3) have been prepared through a
one-pot reaction starting from the primary arylamine, which
are employed for hydrolysis, by using H2O as the source and
aniline as the HCl acceptor, both of two equivalents, to give
hydridosilanediols RSiH(OH)2 (R = N(SiMe2Ph)-2,6-iPr2C6H3
(4), N(SiMe3)-2,6-iPr2C6H3 (5), and N(SiMe2Ph)-2,4,6-Me3C6H2
(6)), in good to excellent yields, under control from 0 °C to
room temperature. Compound 4 reacted with AlMe3, AliBu3,
AlH(iBu)2, and AlH3·NMe3 to give compounds 7 and 9–11,
respectively, and 5 with AlMe3 to give compound 8. Com-
pounds 7–9 and 11 are characterized to have cyclic structures
all with a core of Si2O4Al2 and compound 10 has a bicyclic
structure with a core of Si3O6Al2. Compound 10 exhibits a new
structure type among the ring5d,20,22 and cage5a,d,20,22
compounds reported as the well-defined structural models of
the aluminosilicates such as feldspars and zeolites.3 Notably,
compounds 7–11 all bear the SiH groups and are considered
to be alumino(hydrido)siloxanes. This is a novel type of
aluminosiloxane that has not been prepared so far. Hydrido-
silica has been proved to reduce Ag(I) into molecularly scaled
Ag(0) nanoclusters by means of SiH functionality.11 Hydrido-
silanediol (4) is able to transform Cu(I) and Ag(I) into their
metal nanocrystals as well. But, 4 (or 5) enables the formation
of alumino(hydrido)siloxanes (7–11) all bearing the hydrido
group at the Si center. Compounds 7–11 may have potential in
preparing the transition metal nanoclusters dispersed on the
pore walls of the aluminosilicate microspheres.
Fig. 4 X-ray crystal structure of 10. H atoms except for those of SiH are
omitted for clarity. Selected bond lengths (Å) and angles (°): Si(1)–H(1)
1.35(4), Si(2)–H(2) 1.36(3), Si(3)–H(3) 1.42(4), Si(1)–O(1) 1.599(3), Si(1)–
O(2) 1.610(3), Si(2)–O(3) 1.604(3), Si(2)–O(4) 1.615(3), Si(3)–O(5)
1.609(3), Si(3)–O(6) 1.618(3), Al(1)–O(1) 1.707(3), Al(1)–O(4) 1.716(3),
Al(1)–O(5) 1.718(3), Al(2)–O(2) 1.718(3), Al(2)–O(3) 1.717(3), Al(2)–O(6)
1.711(3); O(1)–Si(1)–O(2) 112.4(1), O(3)–Si(2)–O(4) 111.9(1), O(5)–Si(3)–
O(6) 113.8(1), O(1)–Al(1)–O(4) 113.4(2), O(1)–Al(1)–O(5) 112.5(2), O(4)–
Al(1)–O(5) 114.8(2), O(2)–Al(2)–O(3) 113.6(2), O(2)–Al(2)–O(6) 115.4(1),
O(3)–Al(2)–O(6) 112.0(1), Si(1)–O(1)–Al(1) 145.3(2), Si(1)–O(2)–Al(2)
128.9(2), Si(2)–O(3)–Al(2) 144.3(2), Si(2)–O(4)–Al(1) 132.8(2), Si(3)–O(5)–
Al(1) 134.4(2), Si(3)–O(6)–Al(2) 138.5(2).
Fig. 5 X-ray crystal structure of 11. H atoms except for those of SiH and
AlH are omitted for clarity. Selected bond lengths (Å) and angles (°):
Si(1)–H(2) 1.39(2), Si(1)–O(1) 1.601(2), Si(1)–O(2) 1.606(1), Al(1)–H(1) 1.56
(2), Al(1)–O(1) 1.709(1), Al(1)–O(2A) 1.714(1); O(1)–Si(1)–O(2) 112.6(8),
O(1)–Al(1)–O(2A) 115.4(7), Si(1)–O(1)–Al(1) 147.7(1), Si(1)–O(2)–Al(1A)
145.7(1). Symmetry code for A: −x, −y + 2, −z.
Experimental
Materials and methods
= Ph or OtBu)22e and cage ([2,6-iPr2C6H3N(SiMe3)SiO3]2[AlMe
(THF)]3,5d [(2,6-Me2C6H3)N(SiMe3)SiO3Al(dioxane)]4,22b and
[2,6-iPr2C6H3N(SiMe3)SiO3]2[AliBu(THF)]4)22a structures, com-
pound 10 represents a new type.
Si2O4Al2 as either the core in 8–9 and 11 or a core part in 10
can be considered as one of the basic unit rings widely existing
in aluminosilicates.3b Within the ring, both the Al and the Si
All manipulations were carried out under a dry argon or nitro-
gen atmosphere by using Schlenk line and/or glovebox tech-
niques. The solvents toluene, n-hexane, and tetrahydrofuran
were dried by refluxing with sodium/potassium benzophenone
under an N2 atmosphere prior to use. The NMR (1H, 13C, and
29Si) spectra were recorded on a Bruker Avance II 400 or
500 MHz spectrometer. The melting point of the compound was
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1
measured in a sealed glass tube using a Büchi-540 instrument. product. Yield: 14.8 g, 80%. H NMR (500 MHz, CDCl3, 298 K,
Elemental analysis was performed on a Thermo Quest Italia SPA ppm): δ = 0.78 (s, 6 H, SiMe2), 2.45 (s, 6 H, o-Me), 2.47 (s, 3 H,
EA 1110 instrument. Commercially available reagents were p-Me), 5.80 (s, 1 H, SiH), 7.08 (s), 7.52–7.66 (m), 7.80–7.85 (m)
purchased from Aldrich, Acros, Alfa-Assar and used as received. (7 H, C6H5 and C6H2). 13C{1H} NMR (100 MHz, C6D6, 298 K,
AlH3·NMe3 was prepared according to a published procedure.24
ppm): δ = −0.3 (SiMe2), 20.3 (o-Me), 20.8 (p-Me), 128.0, 130.0,
2,6-iPr2C6H3N(SiMe2Ph)SiHCl2 (1). At −78 °C, nBuLi 130.1, 134.6, 135.3, 137.0, 137.1, 137.5 (C6H2 and C6H5). 29Si
(20.83 mL, 2.4 M solution in n-hexane, 50 mmol) was added {1H} NMR (99 MHz, CDCl3, 298 K, ppm): δ = −23.0 (SiHCl2),
dropwise to a solution of 2,6-iPr2C6H3NH2 (9.43 mL, 50 mmol) 1.6 (SiMe2Ph). IR (KBr plate, cm−1): ˜ν = 2223 (Si–H). Anal.
in diethyl ether (150 mL). The mixture was warmed to room calcd (%) for C17H23Cl2NSi2 (Mr = 368.45): C, 55.42; H, 6.29; N,
temperature and stirred for 12 h to form lithium salt 2,6- 3.80. Found: C, 55.39; H, 6.42; N, 3.74.
iPr2C6H3NHLi. The solution was again cooled to −78 °C, and
2,6-iPr2C6H3N(SiMe2Ph)SiH(OH)2 (4). At
0
°C, H2O
PhMe2SiCl (8.27 mL, 50 mmol) was added to it. After the (1.17 mL, 65 mmol) was added dropwise to a violently stirring
mixture was warmed to room temperature and stirred for 12 h, mixture of 1 (13.3 g, 32.5 mmol) and PhNH2 (6.05 g, 65 mmol)
compound 2,6-iPr2C6H3NH(SiMe2Ph) was formed, which in diethyl ether (300 mL). The mixture was allowed to warm to
was used for further reaction without isolation. The room temperature and stirred for an additional 5 h. Large
2,6-iPr2C6H3NH(SiMe2Ph)-containing mixture was cooled amounts of PhNH2·HCl were generated and filtered off. The fil-
again to −78 °C, and nBuLi (20.83 mL, 2.4 M solution in trate was evaporated to dryness and the residue was collected
n-hexane, 50 mmol) was added to it. The mixture was warmed and washed with cooled n-hexane (−20 °C, 3 mL) to give an
to room temperature and stirred for 12 h to give lithium salt off-white solid of 4. Yield: 11.6 g, 95%. Mp: 97 °C. 1H NMR
2,6-iPr2C6H3N(SiMe2Ph)Li. By cooling again to −78 °C, neat (500 MHz, CDCl3, 298 K, ppm): δ = 0.40 (s, 6 H, SiMe2), 1.14 (d,
3
SiCl3H (5 mL, 50 mmol) was added to this mixture. This 3JHH = 6.8 Hz, 6 H, CHMe2), 1.18 (d, JHH = 6.8 Hz, 6 H,
3
mixture was warmed to room temperature and stirred for 12 h. CHMe2), 2.47 (br, 2 H, Si(OH)2), 3.49 (sept, JHH = 6.8 Hz, 2 H,
All the insoluble solids produced were filtered off and the fil- CHMe2), 4.55 (s, 1 H, SiH), 7.09–7.19 (m), 7.36–7.45 (m),
trate was evaporated to dryness under reduced pressure. The 7.65–7.72 (m) (8 H, C6H3 and C6H5). 13C{1H} NMR (126 MHz,
residue was extracted with n-hexane (15 mL) and the extract CDCl3, 298 K, ppm): δ = −0.5 (SiMe2), 24.1, 25.6 (CHMe2), 28.1
was kept at −20 °C. After 24 h, colorless crystals of 1 were (CHMe2), 124.1, 125.7, 128.0, 129.7, 134.3, 137.8, 139.1, 147.8
formed and collected by filtration. Yield: 13.3 g, 65%. Mp: (C6H3 and C6H5). 29Si{1H} NMR (99 MHz, CDCl3, 298 K, ppm):
42 °C. 1H NMR (500 MHz, CDCl3, 298 K, ppm): δ = 0.53 (s, 6 H, δ = −45.7 (SiH(OH)2), −1.9 (SiMe2Ph). IR (KBr plate, cm−1): ˜ν =
3
3
SiMe2), 1.08 (d, JHH = 6.8 Hz, 6 H, CHMe2), 1.11 (d, JHH = 6.8 3550, 3359 (Si–OH), 2200 (Si–H). Anal. calcd for C20H31NO2Si2
3
Hz, 6 H, CHMe2), 3.53 (sept, JHH = 6.8 Hz, 2 H, CHMe2), 5.39 (Mr = 373.19): C, 64.29; H, 8.36; N, 3.75. Found: C, 64.17; H,
(s, 1 H, SiH), 7.07–7.22 (m), 7.30–7.41 (m), 7.48–7.53 (m) (8 H, 8.59; N, 3.86.
C6H3 and C6H5). 13C{1H} NMR (126 MHz, CDCl3, 298 K, ppm):
2,6-iPr2C6H3N(SiMe3)SiH(OH)2 (5). At 0 °C, H2O (1.08 mL,
δ = −0.10 (SiMe2), 23.6, 26.3 (CHMe2), 28.3 (CHMe2), 124.4, 60 mmol) was added dropwise to a violently stirring mixture of
126.8, 127.9, 130.0, 134.7, 136.3, 137.4, 147.8 (C6H3 and C6H5). 2 (10.4 g, 30 mmol) and PhNH2 (5.59 g, 60 mmol) in diethyl
29Si{1H} NMR (99 MHz, CDCl3, 298 K, ppm): δ = −21.5 ether (300 mL). After addition, the mixture was allowed to
(SiHCl2), 1.2 (SiMe2Ph). IR (KBr plate, cm−1): ˜ν = 2228 (Si–H). warm to room temperature and stirred for an additional 5 h.
Anal. calcd for C20H29Cl2NSi2 (Mr = 410.52): C, 58.51; H, 7.12; Large amounts of PhNH2·HCl were generated and filtered off.
N, 3.41. Found: C, 58.80; H, 7.18; N, 3.59.
The filtrate was evaporated to dryness and the residue was col-
2,6-iPr2C6H3N(SiMe3)SiHCl2 (2). Complex 2 was prepared in lected and washed with cooled n-hexane (−20 °C, 3 mL) to give
1
a similar manner to that of 1, and in the preparation Me3SiCl an off-white solid of 5. Yield: 8.1 g, 87%. Mp: 116 °C. H NMR
(6.3 mL, 50 mmol) was used instead of Me2PhSiCl. Complex 2 (500 MHz, CDCl3, 298 K, ppm): δ = 0.14 (s, 9 H, SiMe3), 1.18 (d,
3
was obtained as an off-white solid. Yield: 10.8 g, 62%. Mp: 3JHH = 6.8 Hz, 6 H, CHMe2), 1.22 (d, JHH = 6.8 Hz, 6 H,
3
35 °C. 1H NMR (500 MHz, CDCl3, 298 K, ppm): δ = 0.23 (s, 9 H, CHMe2), 2.48 (br, 2 H, Si(OH)2), 3.49 (sept, JHH = 6.8 Hz, 2 H,
3
3
SiMe3), 1.18 (d, JHH = 6.8 Hz, 6 H, CHMe2), 1.26 (d, JHH = 6.8 CHMe2), 4.69 (s, 1 H, SiH), 7.06–7.17 (m, 3 H, C6H3). 13C{1H}
3
Hz, 6 H, CHMe2), 3.41 (sept, JHH = 6.8 Hz, 2 H, CHMe2), 5.50 NMR (100 MHz, CDCl3, 298 K, ppm): δ = 1.6 (SiMe3), 24.4, 25.5
(s, 1 H, SiH), 7.03–7.33 (m, 3 H, C6H3). 13C{1H} NMR (CHMe2), 28.0 (CHMe2), 124.1, 125.5, 138.2, 147.6 (C6H3). 29Si
(126 MHz, CDCl3, 298 K, ppm): δ = 1.7 (SiMe3), 24.3, 26.0 {1H} NMR (99 MHz, CDCl3, 298 K, ppm): δ = −46.4 (SiH(OH)2),
(CHMe2), 28.2 (CHMe2), 124.4, 126.7, 137.8, 147.6 (C6H3). 29Si 7.1 (SiMe3). IR (KBr plate, cm−1): ˜ν = 3554, 3319 (Si–OH), 2201
{1H} NMR (99 MHz, CDCl3, 298 K, ppm): δ = −22.0 (SiHCl2), (Si–H). Anal. calcd for C15H29NO2Si2 (Mr = 311.17): C, 57.82; H,
11.2 (SiMe3). IR (KBr plate, cm−1): ˜ν = 2254 (Si–H). Anal. calcd 9.38; N, 4.50. Found: C, 57.64; H, 9.42; N, 4.55.
for C15H27Cl2NSi2 (Mr = 348.46): C, 51.70; H, 7.81; N, 4.02.
2,4,6-Me3C6H2N(SiMe2Ph)SiH(OH)2 (6). At
0
°C, H2O
Found: C, 51.55; H, 7.91; N, 3.62.
(1.08 mL, 60 mmol) was added dropwise to a violently stirring
2,4,6-Me3C6H2N(SiMe2Ph)SiHCl2 (3). Complex 3 was pre- solution of 3 (11.0 g, 30 mmol) and PhNH2 (5.5 mL, 60 mmol)
pared in a similar manner to that of 1, and in the preparation in Et2O (300 mL). After addition, the mixture was allowed to
2,4,6-Me3C6H2NH2 (7.04 mL, 50 mmol) was used instead of warm to room temperature and stirred for an additional 40 h.
2,6-iPr2C6H3NH2. Complex 3 was obtained as a colorless oily Large amounts of PhNH2·HCl were generated and filtered off.
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The filtrate was evaporated to dryness and the residue was
[2,6-iPr2C6H3N(SiMe2Ph)Si(H)O2AliBu(THF)]2 (9). At room
extracted into n-hexane (15 mL). The extract was kept at temperature, AliBu3 (2.0 mL of 1 M solution in toluene,
−20 °C. 48 h later, colorless crystals of 6 were formed, which 2.0 mmol) was added dropwise to a violently stirring solution
were collected by filtration. Yield: 7.6 g, 76%. Mp: 43 °C. 1H of 4 (0.746 g, 2.0 mmol) in THF (20 mL). After addition, the
NMR (500 MHz, CDCl3, 298 K, ppm): δ = 0.36 (s, 6 H, SiMe2), mixture was stirred for 15 h. All volatiles were removed under
2.22 (s, 6 H, o-Me), 2.23 (s, 3 H, p-Me), 2.39 (br, 2 H, Si(OH)2), reduced pressure, and the residue was collected and washed
4.58 (s, 1 H, SiH), 6.84 (s), 7.33–7.43 (m), 7.64–7.72 (m) (7 H, with cooled n-hexane (−20 °C, 1 mL) to give an off-white solid
C6H5 and C6H2). 13C{1H} NMR (100 MHz, C6D6, 298 K, ppm): of 9. Yield: 0.65 g, 62%. Mp: 157 °C. 1H NMR (500 MHz,
δ = 0.1 (SiMe2), 20.4 (o-Me), 20.8 (p-Me), 128.0, 129.5, 129.7, CDCl3, 298 K, ppm): δ = −0.24 (m, 4 H, AlCH2CH(CH3)2,
134.0, 134.4, 137.4, 138.7, 140.1 (C6H2 and C6H5). 29Si{1H} 0.03–0.18 (m), 0.44 (s), 0.85–1.17 (m), 1.24–1.31 (m) (48 H,
NMR (99 MHz, CDCl3, 298 K, ppm): δ = −47.2 (SiH(OH)2), −1.7 SiMe2, AlCH2CH(CH3)2, and CHMe2), 1.66 (m,
8
H,
(SiMe2Ph). IR (KBr plate, cm−1): ˜ν = 3574, 3280 (Si–OH), 2198 THF-OCH2CH2), 1.81 (m, 2 H, AlCH2CH(CH3)2), 3.18–3.83 (m,
(Si–H). Anal. calcd (%) for C17H25NO2Si (Mr = 331.56): C, 61.58; 12 H, CHMe2 and THF-OCH2CH2), 4.58 (s, 2 H, SiH), 6.95 (s),
1
H, 7.60; N, 4.22. Found: C, 61.49; H, 7.76; N, 4.33.
7.14–7.32 (m), 7.53–7.76 (m) (16 H, C6H3 and C6H5). H NMR
[2,6-iPr2C6H3N(SiMe2Ph)Si(H)O2AlMe(THF)]2 (7). At room (500 MHz, d6-DMSO, 298 K, ppm): δ = −0.32 (m, 4 H, AlCH2CH
3
temperature, AlMe3 (1.0 mL of 1 M solution in n-hexane, (CH3)2, 0.23 (s, 12 H, SiMe2), 0.83 (d, JHH = 6.6 Hz, 12 H,
1.0 mmol) was added dropwise to a violently stirring solution AlCH2CH(CH3)2), 0.91 (d, 3JHH = 6.8 Hz, 12 H, CHMe2), 1.09 (d,
3
of 4 (0.373 g, 1.0 mmol) in THF (20 mL). After addition, the 3JHH = 6.8 Hz, 12 H, CHMe2), 1.71 (sept, JHH = 6.6 Hz, 2 H,
mixture was stirred for 15 h. All volatiles were removed under AlCH2CH(CH3)2, 1.77 (m, 8 H, THF-OCH2CH2), 3.60 (m, 8 H,
reduced pressure, and the residue was collected and washed THF-OCH2CH2), 3.66 (sept, 3JHH = 6.8 Hz, 4 H, CHMe2), 4.55 (s,
with cooled n-hexane (−20 °C, 1 mL) to give an off-white solid 2 H, SiH), 6.94 (s), 7.17–7.31 (m), 7.56–7.64 (m) (16 H, C6H3
of 7. Yield: 0.32 g, 66%. Mp: 167 °C. 1H NMR (500 MHz, and C6H5). 13C{1H} NMR (126 MHz, d6-DMSO, 298 K, ppm): δ =
CDCl3, 298 K, ppm): δ = –1.00 (s, 6 H, AlMe), 0.29 (s, 12 H, 0.8 (SiMe2), 24.0, 25.4, 25.7, 27.0, 28.2 (AlCH2CHMe2 and
SiMe2), 1.05 (d, 3JHH = 6.8 Hz, 12 H, CHMe2), 1.10 (d, 3JHH = 6.8 CHMe2), 25.1 (THF-OCH2CH2), 67.0 (THF-OCH2CH2), 122.7,
Hz, 12 H, CHMe2), 1.74 (m, 8 H, THF-OCH2CH2), 3.44 (m, 8 H, 123.6, 126.8, 127.9, 134.1, 141.0, 141.2, 147.5 (C6H3 and C6H5).
THF-OCH2CH2), 3.64 (br, 4 H, CHMe2), 4.55 (s, 2 H, SiH), 6.97 29Si{1H} NMR (99 MHz, CDCl3, 298 K, ppm): δ = −65.1 (SiH
(s), 7.20–7.29 (m), 7.56–7.64 (m) (16 H, C6H3 and C6H5). 13C (O)), −5.5 (SiMe2Ph). IR (KBr plate, cm−1): ˜ν = 2109 (Si–H).
{1H} NMR (126 MHz, CDCl3, 298 K, ppm): δ = −14.0 (AlMe), 0.1 Anal. calcd for C56H92Al2N2O6Si4 (Mr = 1055.64): C, 63.71; H,
(SiMe2), 24.0 (THF-OCH2CH2), 25.2, 25.9 (CHMe2), 27.9 8.78; N, 2.65. Found: C, 63.56; H, 8.75; N, 2.75. X-ray quality
(CHMe2), 70.3 (THF-OCH2CH2), 123.1, 123.6, 127.1, 128.4, single-crystals of 9 were obtained by recrystallization in
134.7, 141.1, 142.3, 148.2 (C6H3 and C6H5). 29Si{1H} NMR n-hexane at −20 °C.
(99 MHz, CDCl3, 298 K, ppm): δ = −66.2 (SiH(O)), −5.8
[2,6-iPr2C6H3N(SiMe2Ph)Si(H)O2]3[Al(THF)]2 (10). At room
(SiMe2Ph). IR (KBr plate, cm−1): ˜ν = 2120 (Si–H). Anal. calcd for temperature, AlHiBu2 (1.0 mL of 1 M solution in toluene,
C50H80Al2N2O6Si4 (Mr = 971.48): C, 61.82; H, 8.30; N, 2.88. 1.0 mmol) was added dropwise to a violently stirring solution
Found: C, 61.73; H, 8.41; N, 2.82.
of 4 (0.56 g, 1.5 mmol) in THF (20 mL). After addition, the
[2,6-iPr2C6H3N(SiMe3)Si(H)O2AlMe(THF)]2 (8). At room mixture was stirred for 15 h. All volatiles were removed under
temperature, AlMe3 (2.0 mL of 1 M solution in n-hexane, reduced pressure, and the residue was collected and washed
2.0 mmol) was added dropwise to a violently stirring solution with cooled n-hexane (−20 °C, 1 mL) to give an off-white solid
of 5 (0.622 g, 2.0 mmol) in THF (20 mL). After addition, the of 10. Yield: 0.42 g, 64%. Mp: 147 °C. 1H NMR (500 MHz,
3
mixture was stirred for 15 h. All volatiles were removed under CDCl3, 298 K, ppm): δ = 0.21 (s, 18 H, SiMe2), 1.04 (d, JHH
=
3
reduced pressure, and the residue was collected and washed 6.8 Hz, 18 H, CHMe2), 1.19 (d, JHH = 6.8 Hz, 18 H, CHMe2),
with n-hexane (−20 °C, 1 mL) to give an off-white solid of 8. 1.52 (m, 8 H, THF-OCH2CH2), 3.37 (m, 8 H, THF-OCH2CH2),
3
Yield: 0.60 g, 71%. Mp: 196 °C. 1H NMR (500 MHz, CDCl3, 3.86 (sept, JHH = 6.8 Hz, 6 H, CHMe2), 5.04 (s, 3 H, SiH), 7.02
298 K, ppm): δ = −1.00 (s, 6 H, AlMe), 0.03 (s, 18 H, SiMe3), (s), 7.19–7.26 (m), 7.78–7.86 (m) (24 H, C6H3 and C6H5). 13C
3
3
1.14 (d, JHH = 6.8 Hz, 12 H, CHMe2), 1.17 (d, JHH = 6.8 Hz, {1H} NMR (126 MHz, CDCl3, 298 K, ppm): δ = 1.5 (SiMe2), 24.7,
12 H, CHMe2), 1.83 (m, 8 H, THF-OCH2CH2), 3.46–3.88 (m, 25.9 (CHMe2), 24.9 (THF-OCH2CH2), 27.7 (CHMe2), 72.3
12 H, CHMe2, THF-OCH2CH2), 4.64 (s, 2 H, SiH), 6.84–7.16 (m, (THF-OCH2CH2), 123.3, 124.0, 127.0, 127.8, 134.8, 140.7, 143.0,
6 H, C6H3). 13C{1H} NMR (126 MHz, CDCl3, 298 K, ppm): δ = 148.4 (C6H3 and C6H5). 29Si{1H} NMR (99 MHz, CDCl3, 298 K,
−14.1 (AlMe), 1.7 (SiMe3), 24.2 (THF-OCH2CH2), 25.2, 25.7 ppm): δ = −59.3 (SiH(O)), −3.5 (SiMe2Ph). IR (KBr plate, cm−1):
(CHMe2), 27.9 (CHMe2), 70.3 (THF-OCH2CH2), 122.9, 123.2, ˜ν = 2134 (Si–H). Anal. calcd for C68H103Al2N3O8Si6 (Mr
=
143.1, 148.0 (C6H3). 29Si{1H} NMR (99 MHz, CDCl3, 298 K, 1313.04): C, 62.20; H, 7.91; N, 3.20. Found: C, 62.44; H, 8.06;
ppm): δ = −66.5 (SiH(O)), 2.5 (SiMe3). IR (KBr plate, cm−1): ˜ν = N, 3.21. X-ray quality single-crystals of 10 were obtained by
2107 (Si–H). Anal. calcd for C40H76Al2N2O6Si4 (Mr = 847.34): C, recrystallization in n-hexane at −20 °C.
56.70; H, 9.04; N, 3.31. Found: C, 56.98; H, 8.97; N, 3.32. X-ray
[2,6-iPr2C6H3N(SiMe2Ph)Si(H)O2AlH(THF)]2 (11). At −20 °C,
quality single-crystals of 8 were obtained by recrystallization in a solution of AlH3·NMe3 (0.0445 g, 0.5 mmol) in THF (20 mL)
n-hexane at −20 °C.
was added dropwise to a violently stirring solution of 4
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(0.187 g, 0.5 mmol) in THF (5 mL). After addition, the mixture exposure to Mo-Ka radiation. A summary of cell parameters,
was allowed to warm to room temperature and stirred for 15 h. data collection, and structure solution and refinements is
All volatiles were removed under reduced pressure, and the given in Table S1 in the ESI.†
residue was extracted with a solvent mixture of n-hexane
(2 mL) and THF (2 mL). The extract was kept at −20 °C for 48 h
and colorless crystals of 11 were formed. Yield: 0.16 g, 68%.
Acknowledgements
1
Mp: 135 °C. H NMR (400 MHz, CDCl3, 298 K, ppm): δ = 0.30
3
(s, 12 H, SiMe2), 1.05 (d, JHH = 6.8 Hz, 12 H, CHMe2), 1.12 (d, This work is supported by the National Nature Science Foun-
3JHH = 6.8 Hz, 12 H, CHMe2), 1.78 (m, 8 H, THF-OCH2CH2), dation of China (21473142 and 91027014), the National Basic
3.31 (br, 2 H, AlH), 3.51 (m, 8 H, THF-OCH2CH2), 3.65 (sept, Research Program of China (2012CB821704), and the Program
3JHH = 6.8 Hz, 4 H, CHMe2), 4.58 (s, 2 H, SiH), 6.98 (s), for Innovative Research Team in Chinese Universities
7.18–7.35 (m), 7.59–7.69 (m) (16 H, C6H3 and C6H5). 13C{1H} (2013B019 and IRT_14R31).
NMR (126 MHz, CDCl3, 298 K, ppm): δ = 0.2 (SiMe2), 24.1, 26.0
(CHMe2), 25.2 (THF-OCH2CH2), 27.9 (CHMe2), 70.0
(THF-OCH2CH2), 123.1, 123.7, 127.2, 128.4, 134.7, 141.0, 142.0,
Notes and references
148.2 (C6H3 and C6H5). 29Si{1H} NMR (99 MHz, CDCl3, 298 K,
ppm): δ = −65.7 (SiH(O)), −5.4 (SiMe2Ph). IR (KBr plate, cm−1):
˜ν = 2113 (Si–H), 1841 (Al–H). Anal. calcd for C48H76Al2N2O6Si4
(Mr = 943.43): C, 61.11; H, 8.12; N, 2.97. Found: C, 60.63; H,
8.39; N, 2.61. Repetition of this reaction gave a colorless solu-
tion, which afforded suitable X-ray quality single-crystals of 11
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and keeping at −20 °C for ca. 40 h. The 0.34 : 0.66 molar ratio
of THF and NMe3 in this molecule was determined by X-ray
structural analysis.
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Crystallographic data for compounds 6 and 8–11 were collected
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graphite-monochromatic Mo-Ka radiation (λ = 0.71073 Å) was
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