Synthesis of organoaluminum chalcogenides and their applications in Lewis acid catalysis

Article abstract of DOI:10.1016/j.ica.2019.119091

Two chalcogenide bridged bi-aluminum compounds [LAl(NMe₃)(μ-S)Al(NMe₃)L] (1) and [LAl(NMe₃)(μ-Se)Al(NMe₃)L] (2) were synthesized by reacting LAlH(NMe₃) (L = 4-methylbenzylidene-o-aminothiophenol) with

Full text of DOI:10.1016/j.ica.2019.119091

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Synthesis of organoaluminum chalcogenides and their applications in Lewis
acid catalysis
Yi Ding, Xiaoli Ma, Yashuai Liu, Wenqing Liu, Congjian Ni, Ben Yan, Li Yan,
Zhi Yang
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Please cite this article as: Y. Ding, X. Ma, Y. Liu, W. Liu, C. Ni, B. Yan, L. Yan, Z. Yang, Synthesis of
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Synthesis of organoaluminum chalcogenides and their applications
in Lewis acid catalysis
Yi Ding a, Xiaoli Ma *, a, Yashuai Liu a, Wenqing Liu a, Congjian Ni a, Ben Yan a, Li
Yan a, Zhi Yang *, a
a
School of Chemistry and Chemical Engineering, Beijing Institute of Technology, 100081 Beijing, P.
R. China
Fax: (+86) 10-68911032; E-mail: maxiaoli@bit.edu.cn; zhiyang@bit.edu.cn.
Highlights
1) Synthesized and fully characterized two new chalcogenide bridged bi-aluminum
compounds.
2) New compounds are used for Lewis acid catalysis.
3) Bi-aluminum compounds have excellent catalytic activity in cyanosilylation of
aldehydes.
ABSTRACT
Two chalcogenide bridged bi-aluminum compounds [LAl(NMe3)(μ-S)Al(NMe3)L] (1)
and [LAl(NMe3)(μ-Se)Al(NMe3)L] (2) were synthesized by reacting LAlH(NMe3) (L =
4-methylbenzylidene-o-aminothiophenol) with one equivalent of sulfur and selenium
without any catalysts in ambient temperature. Compounds 1 and 2 have been
characterized by 1H and 13C NMR, elemental analyses, and single crystal X-ray structural
analysis. Furthermore, bi-aluminum compounds 1 or 2 were investigated as Lewis acid
catalyst for the cyanosilylation of aldehydes and the condensation of aldimine and
hydroboration of aldol ketones, respectively.
Keywords:
Organoaluminum chalcogenides; Lewis acid catalysis; cyanosilylation; condensation
1 Introduction

Organoaluminum chalcogenides as important precursors in chemical vapor deposition
(CVD) and as catalysts have attracted great attention [1-4]. In 1993, Roesky and
collaborators reacted selenium and tellurium with [(Cp*Al)4] to report on the first
reactions of organoaluminum compounds with elements from group 16 [5]. In their
seminal contribution, a wide variety of organoaluminum chalcogenides has been
synthesized and showed a well-rounded aluminum chemistry. Most of the
organoaluminum chalcogenides can be classified as (RAlX)n [6-8], RAl(XH)2 [9-12],
RAl(XH)(μ-X)(XH)AlR [10-13], RAl(μ-X)nAlR [12, 14-17], RAlXR' [18-32],
RAl(μ-S)2MR' [33-34] or RAl(μ-X)2Mn(μ-X)2AlR (M = Ge, Sn, or Cu, Ag, Zn) [34-37],
(R, R' = organic group; X =S, Se or Te). Aluminum dihydrides supported by chelating
N-based ligands are the preferred material for the synthesis of most of the above
compounds.
Further
reactions
of
the
dimeric
chalcogenidoalane
{[ArNH(CH2)3NAr]Al(μ-E)}2 (E = S, Se or Te) [38] and trans-[{Me3N(H)Al(μ-E)}2] (E
= Se or Te) [39] with chalcogen or organochalcogenides have been investigated.
However, the reactions of aluminum monohydride with chalcogens, which might
generate the corresponding monomeric Al-EH moieties, have not been reported so far.
Therefore, we became interested in the reactions of aluminum monohydride with group
16 elements.
In 1950, Ziegler and Natta have made pioneering advances in research and industrial
innovation which greatly simplified the production of polyolefins. The research on the
catalytic properties of aluminum has attracted much attention of scientists [40-44].
Entering the 21st century, more and more chemists came to a consensus that main group
compounds can imitate the behavior of transition metal complexes [45-49]. Since 2015,
we have reported on aluminum-hydride types that catalyzed the hydroboration of
compounds with unsaturated bonds [50-51]. The research on the catalytic properties of
organoaluminum compounds including Al/P-based FLPs (frustrated Lewis pairs) that
activate small molecules is developing rapidly [52-65]. However, most of them focus on

mono-aluminum catalysis, which means that one aluminum center catalyzes the reactions,
while bi-aluminum catalysis has rarely been reported.
Herein, we report on the synthesis and structural characterization of a monomeric
aluminum monohydride reacting with the group 16 elements sulfur and selenium to give
chalcogenide-bridged organoaluminum compounds. These compounds act as Lewis acid
catalysts in the cyanosilylation of aldehydes, in aldimine condensation reaction and in
hydroboration reactions, respectively.
2 Results and discussion
2.1 Synthesis and characterization
As shown in Scheme 1, LAlH(NMe3) reacts smoothly with one equivalent of
elemental
sulfur
and
selenium
at
room
temperature
to
afford
[LAl(NMe3)(μ-S)Al(NMe3)L] (1) and [LAl(NMe3)(μ-Se)Al(NMe3)L] (2). It is
noteworthy that 1 or 2 is formed even when more equivalents of chalcogenides are used.
The crystals of 1 and 2 are slightly soluble in common organic solvents such as toluene,
dichloromethane, or tetrahydrofuran, respectively. Compounds 1 and 2 were
1
13
characterized by H NMR and C NMR spectroscopy, single crystal X-ray structural
analysis as well as elemental analysis.
The 1H NMR spectra of 1 or 2 show a diastereotopic splitting of the CH2 resonances of
the benzyl groups with a coupling between both hydrogen atoms, two resonances of the
N(CH3)3 groups, and two resonances for the methyl substituents at the aryl groups,
indicating a chiral surrounding of the aluminum atoms in compounds 1 and 2.
Scheme 1 Synthesis of 1 and 2.
2.2 Crystal structures
The molecular geometries of 1 and 2 were determined by X-ray crystallography.

Compounds 1 and 2 crystallized in the triclinic space group P-1. The molecular structures
of 1 and 2 are shown in Figure 1 and 2. According to the molecular structures, both
aluminum atoms have a chiral surrounding, which make them diastereomers. The spatial
configuration of compounds 1 and 2 can be easily determined as R, R and S, S,
respectively. The structures of 1 and 2 are elucidated by crystallographic studies to
contain a pseudo twofold rotation axis through the chalcogen atoms. Every aluminum
atom is four-coordinated and is surrounded by a nitrogen atom and a sulfur atom on the
ligand, one nitrogen atom from the NMe3 group and one bridged chalcogenide atom
sulfur or selenium. The Al atom deviates slightly from the SCCN plane of the ligand due
to the Al←NMe3 coordination. As a result of the sterically demanding ligands the
aluminum center adopts a distorted tetrahedral geometry.
Figure 1 Molecular structure of LAl(NMe3)(μ-S)Al(NMe3)L (1); hydrogen atoms and solvent molecules are omitted
for clarity; selected bond lengths [Å] and angles [˚]: Al(1)−S(1) 2.2231(15), Al(1)−S(2) 2.1827(15), Al(2)−S(3)
2.2219(18), Al(2)−S(2) 2.1962(17), Al(1)−N(1) 1.817(4), Al(1)−N(6) 1.989(3), Al(2)−N(2) 1.809(4), Al(2)−N(5)
1.990(4) Å; Al(1)−S(2)−Al(2) 102.11(6), S(1)−Al(1)−S(2) 125.29(7), S(3)−Al(2)−S(2) 126.23(7), N(1)−Al(1)−N(6)
106.29(15), S(1)−Al(1)−N(1) 94.20(11), S(1)−Al(1)−N(6) 108.23(13), S(2)−Al(1)−N(1) 115.92(12), S(2)−Al(1)−N(6)
105.47(12), N(2)−Al(2)−N(5) 107.89(15)°.
The bridging sulfur or selenium atom forms chalcogenide-metal bonds with aluminum,
and the Al−(μ-S) bond lengths (2.1941(18) and 2.1840(15) Å) in Al-S-Al of 1 are a little
longer compared to those reported in the literature: L′Al(SH)(μ-S)(SH)AlL′ (2.163(3) and
2.153(3) Å) [13]. The Al−Se bond lengths (2.3263(8) and 2.3233(8) Å) in 2 are almost
identical to those in L′′Al(SeH)(μ-Se)(SeH)AlL′′ (2.326(2) and 2.333 Å) [10]. The

Al-Se-Al angle in 2 (97.81(3)º) is less obtuse than the Al-S-Al angle in 1 (102.06º),
probably because of the longer Al-(μ-Se) distances and the resulting larger separation
between the organic ligands. The Al-S-Al angle in 1 is smaller than those in
[(SiMe3)2CH]2Al(μ-S)Al[(SiMe3)2CH]2 (117.5º) [66] and L′′′Al(SH)(μ-S)(SH)AlL′′′
(110.8º) [13]. The Al-Se-Al angle in 2 is also smaller than those in
[(SiMe3)2CH]2Al(μ-Se)Al[(SiMe3)2CH]2 (114.71º) [67] and L′′Al(SeH)(μ-Se)(SeH)AlL′′
(116.88º) [10].
Figure 2 Molecular structure of LAl(NMe3)(μ-Se)Al(NMe3)L (2); hydrogen atoms and solvent molecules are omitted
for clarity; selected bond lengths [Å] and angles [˚]: Se(1)−Al(3) 2.3263(8), Se(1)−Al(4) 2.3233(8), S(1)−Al(3)
2.2296(10), S(2)−Al(4) 2.2259(9), N(1)−Al(3) 1.998(2), N(7)−Al(3) 1.822(2), N(2)−Al(4) 1.993(2), N(8)−Al(4)
1.827(2) Å; Al(3)−Se(1)−Al(4) 97.81(3), S(1)−Al(3)−Se(1) 126.27(7), S(1)−Al(3)−N(1) 107.24(7), S(1)−Al(3)−N(7)
93.81(7), N(1)−Al(3)−N(7) 107.37(10), Se(1)−Al(3)−N(1) 103.48(7), Se(1)−Al(3)−N(7) 117.46(7), S(2)−Al(3)−Se(1)
124.89(4), N(2)−Al(4)−N(8) 106.35(9)°.
2.3 Catalytic performance
In 2015, we reported on an aluminum complex incorporating soft donors that exhibited
excellent catalytic activity in addition reactions of aldehydes with trimethylsilyl cyanide
(TMSCN) [51]. In 2017, we found that a bi-aluminum compound also showed excellent
catalytic activity in addition reactions of aldehydes with TMSCN [12]. These results
inspired us to develop new bi-aluminum catalysts for such reactions. Herein, we used the
bi-aluminum compounds 1 and 2 to catalyze the cyanosilylation of aldehydes, the

condensation reactions of aldehydes with amines, as well as the hydroborations reaction
of benzaldehyde and acetophenone, respectively.
As shown in Scheme 2, the reaction of TMSCN with aldehydes gave good yields of
products within 4 h with 1 mol% loading of the catalyst at ambient temperature in CDCl3.
The reaction with an aromatic aldehyde exhibited a high yield (Scheme 2, 3a). The
reaction of an aldehyde with an electron-donating aromatic group (3b) exerted a better
yield than that of an unsubstituted aromatic aldehyde (3a), while the reaction of
o-fluorobenzaldehyde with an electron-withdrawing aromatic group resulted in a lower
yield (3d). Further, the reaction with an aliphatic aldehyde (3e) exhibited a lower yield
than those with aromatic aldehydes (3a). The reactions with substrates including
heterocycles (3f and 3g) were also found to be less efficient than those with aromatic
aldehydes (3e).
Scheme 2 Cyanosilylation of aldehydes catalyzed by 1 or 2.
Scheme 3 Aldimine condensation reaction catalyzed by 1.

In order to prove the better catalytic activity of the catalysts, we used 1 to catalyze the
condensation reaction of amines and aldehydes. We found that 1 also showed excellent
catalytic activity in this aldimine condensation reaction. Those results are shown in
Scheme 3 and indicate near-quantitative yields of products within 6 hours.
The hydroboration of benzaldehyde and acetophenone catalyzed by 1 or 2 was also
performed at room temperature and 50 ℃, respectively. (Scheme 4)
Scheme 4 Hydroboration of benzaldehyde or acetophenone catalyzed by 1 or 2.
3 Experimental section
3.1 General information
Unless otherwise noted, all manipulations were performed using a vacuum line and
standard Schlenk techniques with an atmosphere of nitrogen or using glove box
techniques (typically oxygen and moisture were controlled at less than 1 ppm). Organic
solvents toluene and n-hexane were dried by refluxing with sodium/potassium
benzophenone under nitrogen prior to use. Deuterated CDCl3 was degassed, dried with
CaH2, and filtered before use. Commercially available chemicals were purchased from
J&K and used as received. LAlH(NMe3) was prepared as described in the literature [68].
Elemental analyses were performed by the Analytical Instrumentation Center of the
Beijing Institute of Technology. NMR spectra were recorded on a Bruker Ascend TM
400 spectrometer. Melting points were measured in sealed glass tubes.
3.2 Synthesis of [LAl(NMe3)(μ-S)Al(NMe3)L] (1)

A solution of LAlH(NMe3) (0.314 g, 1.0 mmol) in toluene (10 mL) was added drop by
drop to a suspension of sulfur (0.032 g, 1.0 mmol) in toluene (10 mL) at room
temperature. After the addition was complete, stirring of the reaction mixture was
continued for 24 h and filtered. The solution was concentrated to 8 ml and stored at -30
˚C for 3 d to afford 1 as colorless cuboid crystals. Total yield: 0.189 g (27%), Mp 182 ˚C
(decomp.). 1H NMR (400 MHz, CDCl3, 298 K, TMS, δ, ppm 7.36 (dd, 2 H, 3JH-H = 7.6
Hz, 4JH-H = 1.2 Hz, Ar-H), 7.11 (m, 6 H, Ar-H), 6.94 (m, 2 H, Ar-H), 6.84 (t, 2 H, Ar-H),
6.53-6.47 (m, 2 H, Ar-H), 6.41 (dd, 2 H, 3JH-H = 7.6 Hz, 4JH-H = 1.2 Hz, Ar-H), 4.64 (d, 2
H, 2JH-H = 7.6 Hz, NCH2), 4.52 (d, 2 H, 2JH-H = 8 Hz, NCH2), 2.51 (s, 9 H, NMe3), 2.48 (s,
3 H, ArMe), 2.48 (s, 3 H, ArMe), 2.28 (s, 9 H, NMe3); 13C{1H} NMR (100 MHz, CDCl3,
298 K, TMS, δ, ppm  148.1, 136.1, 135.7, 134.3, 130.9, 128.5, 128.3 (2), 128.0, 127.2,
126.3, 126.1, 117.3, 116.1, 115.5, 109.6 (C of Ar), 46.9, 46.3 (NCH2), 36.6, (NMe3) 20.1
(ArMe). C17H22AlN2S1.5. We didn't get satisfactory data of element analysis.
3.3 Synthesis of [LAl(NMe3)(μ-Se)Al(NMe3)L] (2)
Compound 2 was obtained by using the same protocol. The solution was stored at -30
˚C for 2 d to give colorless cuboid crystals of 2 (0.176, yield 21%), Mp 217 ˚C (decomp.).
1H NMR (400 MHz, CDCl3, 298 K, TMS, δ, ppm  7.38 (dd, 2 H, 3JH-H = 7.6 Hz, 4JH-H
= 1.2 Hz, Ar-H), 7.08 (t, 4 H, Ar-H), 6.97 (m, 4 H, Ar-H), 6.85 (m, 4 H, Ar-H), 6.47 (t, 2
H, Ar-H), 4.47 (d, 2 H, 2JH-H = 7.6 Hz, NCH2), 4.08 (d, 2 H, 2JH-H = 7.6 Hz, NCH2), 2.27
(s, 9 H, NMe3), 2.22 (s, 9 H, NMe3) , 2.15 (s, 3 H, ArMe), 1.96 (s, 3 H, ArMe); 13C{1H}
NMR (100 MHz, CDCl3, 298 K, TMS, δ, ppm 147.5, 135.9, 134.8, 134.3, 128.5, 128.3,
128.0, 127.2, 126.3, 116.1, 110.1, 109.6 (C of Ar), 46.9, 46.1 (NCH2), 36.8, (NMe3), 20.1
(ArMe). C34H44Al2N4S2Se·0.25 C7H8 (728.83): calcd. C 58.92, H 6.36, N 7.68; found C
59.16, H 6.66, N 7.41.
3.4 X-ray crystallography
The crystallographic data for compounds 1 and 2 were collected using a Rigaku
AFC10 Saturn 724+ (2×2 bin mode) diffractometer equipped with

graphite-monochromated Mo Kα radiation (λ = 0.71073 Å). Empirical absorption
correction was applied using the SADABS program [69]. Structures were solved by
direct methods [70] and refined by full matrix least squares on F2 using the SHELXL‐97
program [71]. Crystallographic data are provided in Table 1. CCDC 1903169 and
1903170 contain the supplementary crystallographic data for compounds 1 and 2,
respectively, and can be obtained free of charge via www.ccdc.cam.ac.uk/deposit.
Table 1 Crystal data and structure refinement for 1 and 2.
Compound
1
2
Empirical formula
Formula weight
Temperature (K)
Crystal system
Space group
a (Å)
C17H22AlN2S1.5
329.43
C34H44Al2N4S2Se·1.5 C7H8
843.97
296(2)
296(2)
triclinic
triclinic
P-1
P-1
12.3390(19)
14.180(2)
14.347(2)
107.554(5)
109.147(6)
94.791(5)
2214.1(6)
4
12.3667(4)
14.2870(5)
27.3739(9)
93.8100(10)
100.6590(10)
109.1500(10)
4447.7(3)
2
b (Å)
c (Å)
 (°)
 (°)
 (°)
V (Å3)
Z
Dcalcd. (g/cm3)
Absorption coefficient (mm-1)
F(000)
0.988
1.260
0.230
1.012
700
1772
θ range for data collection(°)
Reflections collected
R(int)
2.32 to 26.96
22333
2.30 to 25.70
46029
0.0296
0.0331
Data/restraints/parameters
Goodness-of-fit on F2
Final R1, wR2 [I > 2σ(I)]
R1, wR2 (all data)
8244/26/388
1.109
9969/0/964
1.024
0.0760, 0.1746
0.0367, 0.0912
0.0534, 0.0977
0.538, -0.412
0.0972, 0.1760
Largest difference in peak and hole (e Å−3) 0.741, -1.045
aR = Σ||F0| – |Fc||/Σ|F0|.
2
2
bwR2 = [Σw(F0 – Fc2)2/Σ(F0 )]1/2.

3.5 Hydroboration catalyzed by complexes 1 and 2.
3.5.1 General procedure for the catalytic reactions of aldehydes with TMSCN.
Under N2 atmosphere, a mixture of aldehyde (1 mmol), TMSCN (1 mmol), compound
1 or 2 (0.01 mmol), and CDCl3 (3 ml) were stirred at room temperature. The reaction
time was extended to 4 hours to get satisfying results (Scheme 2). The reaction progress
was monitored by a combination of thin-layer chromatography (TLC) on 0.25 mm Merck
1
silica gel sheets (60F-254) (4×2 cm2) equipped with UV light and H NMR spectral
analysis. After workup, the mixture was allowed to directly pass through a silica-gel
column using a mixture of petroleum ether and ethyl acetate (20:1) as an eluent. The
eluents were collected and then evaporated to dryness to give the desired product that was
13
studied by NMR (1H, C{1H}) and yield calculation. Products 3a - 3f were confirmed
and the spectroscopic data for the products were identical to the reported literature data
[72].
3.5.2 General procedure for the catalytic reactions of aldehydes with amines.
The selected aldehyde (1 mmol) and the chosen amine (1 mmol) were added in CDCl3
(3 ml) consecutively while the catalyst 1 (0.03 mmol) was placed before in the reaction
flask. The resulting mixture was reacted at room temperature within 2 hours (Scheme 3).
The reaction mixture was filtered and the solvent removed under vacuum to yield the
desired product. Quantitative formation of the products given in Scheme 3 were
confirmed, and the spectroscopic data for the products were identical to the reported
literature data [72].
3.5.3 General procedure for the hydroboration of benzaldehyde or acetophenone with
HBpin.
In Scheme 4, the catalyst was added to a solution of benzaldehyde with HBPin (0.155
mL, 1 mmol) in CDCl3 (3 ml) under nitrogen atmosphere. The mixture was placed in a
sealed environment and stirred at room temperature or 50 ℃ for 2 hours. The catalysts
1
include compounds 1 and 2. The products were characterized by H NMR spectroscopy,
and the spectroscopic data for the products were identical to the reported literature data
[51].

Hydroboration of acetophenone catalyzed by compounds 1 and 2 at room temperature
or 50 ℃ utilized a method similar to the one mentioned above except for using a reaction
time of 6 hours.
4 Conclusion
In summary, we have prepared and structurally characterized two new thermally stable
aluminum
chalcogenides
[LAl(NMe3)(μ-S)Al(NMe3)L]
and
[LAl(NMe3)(μ-Se)Al(NMe3)L]. This work shows new strategies for the activation of
chalcogenide-aluminum bonds by aluminum monohydride without any additional catalyst.
Bi-aluminum compounds 1 and 2 act as good Lewis acid catalysts in the cyanosilylation
of aldehydes, in aldimine condensation reactions, as well as in the hydroboration of
benzaldehyde and acetophenone.
Acknowledgement
We gratefully acknowledge financial support of this work by the National Nature Science
Foundation of China (21671018, 21872005).
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Graphical abstract
Organoaluminum chalcogenides [LAl(μ-S)AlL] and [LAl(μ-Se)AlL] were
synthesized and fully characterized. Bi-aluminum as Lewis acidic catalysis
for cyanosilylation and condensation were reported.
Highlights

4) Synthesized and fully characterized two new chalcogenide bridged bi-aluminum
compounds.
5) New compounds are used for Lewis acid catalysis.
6) Bi-aluminum compounds have excellent catalytic activity in cyanosilylation of
aldehydes.