Facile preparation of hydrochlorosilane by alkali metal halide catalyzed Si-H/Si-Cl redistribution reaction

Article abstract of DOI:10.1016/j.tetlet.2020.152235

Various alkali metal halides were found to catalyze the Si-H/Si-Cl redistribution reaction in different polar solvents efficiently. The scope of silane substrate was studied using KF as catalyst and 18-crown-6 as cocatalyst in DMI. The alkali metal halides catalyzed redistribution system provides a useful method to prepare hydrochlorosilanes more facilely. A possible mechanism was proposed to explain the process.

Full text of DOI:10.1016/j.tetlet.2020.152235

Tetrahedron Letters 61 (2020) 152235
Contents lists available at ScienceDirect
Tetrahedron Letters
journal homepage: www.elsevier.com/locate/tetlet
Facile preparation of hydrochlorosilane by alkali metal halide catalyzed
Si-H/Si-Cl redistribution reaction
a,b,
Yi Chen a,b, Yongming Li a, , Caihong Xu
⇑
⇑
a Beijing National Laboratory for Molecular Sciences (BNLMS), Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, PR China
b University of Chinese Academy of Sciences, Beijing 100049, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Various alkali metal halides were found to catalyze the Si-H/Si-Cl redistribution reaction in different
polar solvents efficiently. The scope of silane substrate was studied using KF as catalyst and 18-crown-
6 as cocatalyst in DMI. The alkali metal halides catalyzed redistribution system provides a useful method
to prepare hydrochlorosilanes more facilely. A possible mechanism was proposed to explain the process.
Ó 2020 Elsevier Ltd. All rights reserved.
Received 29 April 2020
Revised 23 June 2020
Accepted 10 July 2020
Available online 19 August 2020
Keywords:
Silicon chemistry
Si-H/Si-Cl redistribution reaction
Hydrochlorosilane preparation
Metal halides catalyst
Hydrochlorosilanes are fundamental organosilicon compounds
in preparation of functional polysiloxanes, polysilazanes, and many
other organosilicon materials [1]. The reactivity of Si-H and Si-Cl of
the molecules endows their wide application in hydrosilylation
reaction and the different nucleophilic substitution reactions
towards the silicon center [2]. There are great demands for
hydrochlorosilanes in industrial fields of rubber, coating, pharma-
ceutical, etc. [3]. However, it has been still kept a synthetic chal-
lenge to prepare these compounds efficiently and facilely.
Many studies have been focused on synthesis of hydrochlorosi-
lanes by selective substitution of hydrogen or chlorine atom at sil-
icon center. With NaBH4 as reductant, dialkyldichlorosilane was
selectively reduced to dialkylhydrochlorosilane successfully [4a],
but the formation of borane during the reaction increases safety
risk and cost of the preparation process. Catalytic hydrogenolysis
of chlorosilanes with iridium or rhodium complex catalyst pro-
vides another way to prepare hydrochlorosilanes [4b,c]. However,
the expensive catalysts restrict practical application of this strat-
egy. On the other hand, selective chlorination of hydrosilanes has
attracted much attention [5]. In 1992, Kunai and co-workers
chlorination of Si-H bond with HCl catalyzed by B(C6F5)3 or B
(C6F5)3/Et2O [5b]. Recently, Sturm reported a Lewis base catalyzed
selective chlorination of hydrosilane with HCl solution [5c].
Although great progress has been made, these methods are mainly
limited to laboratory synthesis, and there is still no disclosed eco-
nomical and convenient industrial process for the preparation of
hydrochlorosilane. Besides, hydrosilanes are usually prepared from
reduction of chlorosilane or alkoxysilane with hydrides reducing
agents. It is a resource waste to some extent that converting Si-H
to Si-Cl by chlorination and producing H2 or other byproducts.
As early as in 1947, Sommer reported the first attempt on
preparation of hydrochlorosilane through the redistribution reac-
tion of hydrosilane and chlorosilane catalyzed by AlCl3 [6a]. Then
the quaternary ammonium salt and tertiary amine were found also
can catalyze the Si-H/Si-Cl redistribution [6b-d]. Both of these cat-
alytic redistribution systems have obvious disadvantages of high
temperature and strict operating conditions. In addition, the sepa-
ration of AlCl3 catalyst from the silane mixture is also difficult.
However, the advantage of high atom utilization efficiency of the
redistribution strategy is very attractive. We have had an interest
in searching for suitable catalysts to overcome the shortcomings
of the redistribution and use its advantages to develop new prepa-
ration routes for hydrochlorosilanes. On the other hand, the work
of Sturm about activation of Si-H bond by Lewis bases also inspired
us [5c]. According to the mode they established, Lewis base, for
example, chloride ion, can activate Si-H bond, then the activated
Si-H bond can easily react with HCl to be chlorinated. We guessed
that the activated Si-H bond by chloride ion maybe also easily
reported
a
convenient method for selective synthesis of
hydrochlorosilane from hydrosilane with CuCl2 as chloride source
and CuI as catalyst [5a]. In 2017, Karina Chulsky disclosed selective
⇑
Corresponding authors at: Beijing National Laboratory for Molecular Sciences
(BNLMS), Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, PR
China (C. Xu).
E-mail address: caihong@iccas.ac.cn (C. Xu).
https://doi.org/10.1016/j.tetlet.2020.152235
0040-4039/Ó 2020 Elsevier Ltd. All rights reserved.

2
Y. Chen et al. / Tetrahedron Letters 61 (2020) 152235
reacted with chlorosilane, so the redistribution reaction between
hydrosilane and chlorosilane may happen. Herein we demon-
strated our effort on realization of a simple and efficient redistribu-
tion system of hydrosilane and chlorosilane, by using the most
readily available and cheapest alkali metal halide as catalyst. This
We then selected DMI as the solvent to optimize the catalyst. It
was found that compared with LiCl, the redistribution reaction
proceeded more slowly using NaCl or KCl as catalyst (see in sup-
porting information Figs. 36–38). Considering all of them can be
completely dissolved in DMI, the difference in reaction rate of
the redistribution may be due to the different solvation effect of
metal cation with the dipolar aprotic solvent, i.e., Li+ has a larger
solvation sheath than Na+ and K+ for its smaller cation size [9a],
which may be more conducive to the dissociation of metal chloride
ion pairs [9b]. The similar catalytic effect of these different metal
chlorides also supports our previous assumption that the dissoci-
ated chloride ion of the catalyst played a key role in this redistribu-
tion process. Besides, it was found that apart from the chlorides,
other common halides, such as KF, KBr, and KI, had similar catalytic
effect on the redistribution (Table 1, entries 14–16). These results
may reflect the similar Si-H bond activation effect of all the halo-
gen ions produced from the dissociation of halides in dipolar apro-
tic solvent. On the other hand, we also found that for the model
substrate system, ClCH2SiH3/ClCH2SiCl3, with each of these halides
salts as catalyst, the redistribution conversion efficiencies of the
reaction were close (Table 1, entries 2, 3, 11–16). As is known,
18-crown-6 was usually used to encapsulate K+ of KF to produce
naked F- for preparation of pentacoordinate silicates [10]. We spec-
ulated that the interaction of 18-crown-6 with K+ may also pro-
mote the redistribution of KF catalytic system and elevate the
redistribution conversion efficiency. Thus, the redistribution reac-
tion of ClCH2SiH3/ClCH2SiCl3 catalyzed by KF/18-crown-6 was car-
ried out to verify the point (Table 1, entries 17–18). Compared with
that of using KF alone as catalyst, the addition of 18-crown-6 as
cocatalyst increased the redistribution conversion of 0.5 h from
52% to 81% (Table 1, entries 13, 17). But no further increase of con-
version efficiency was observed even extending the reaction time
to 3 h. Considering the total yield of hydrochlorosilanes in the
same reaction time, as well as the cost, LiCl and KF/18-crown-6
are preferred catalysts in DMI.
On the basis of the above optimized reaction condition, we then
investigated the substrate scope of the reaction in DMI, with
KF/18-crown-6 or LiCl as the catalyst (Table 2). Various substituted
silane substrates, including chloroalkyl, alkyl, and phenyl silane,
were studied. Except for the systems of Et2SiH2/Et2SiCl2 and Ph2-
SiH2/Ph2SiCl2 (Table 2, entries 7, 8, 12, 13), all the redistribution
reactions proceeded efficiently with the yield mainly ranging from
44% to 71%. The large steric hindrance of double phenyl and ethyl
groups may influence the interaction between substrate and F- and
inhibited the Si-H bond activation effect, while the relatively better
conversion efficiency of Ph2SiH2/Ph2SiCl2 system may be attributed
to the higher electron-withdrawing ability of phenyl than ethyl
(Table 2, entries 7, 8, 12, 13). Compared with that of using LiCl as
catalyst alone, the redistribution conversion catalyzed by KF/18-
crown-6 is 5% higher for the substrates ClCH2SiMeH2/ClCH2-
SiMeCl2 and Cl2CHSiMeH2/Cl2CHSiMeCl2 (Table 2, entries 3–6),
but much lower for the substrates Et2SiH2/Et2SiCl2 and Ph2SiH2/
Ph2SiCl2 (Table 2, entries 7, 8, 12, 13). The results reflected that
KF/18-crown-6 catalytic system may be more easily influenced
by steric hindrance effect. For substrates with less crowded sub-
stituents, the introduction of 18-crown-6 may improve the redis-
tribution conversion slightly. Compared with previously reported
redistribution system [6], the very simple and mild reaction condi-
tion is one of the great advantages of this alkali metal halides cat-
alytic system. To further demonstrate the utility of the new system,
we then carried out a larger scale redistribution reaction to prepare
ClCH2SiMeHCl and Cl2CHSiMeHCl. The pure hydrochlorosilane pro-
duct ClCH2SiMeHCl or Cl2CHSiMeHCl were easily separated
through packed fractional distillation.
maybe will provide
hydrochlorosilanes.
a
more facile way to prepare
We first investigated the possible redistribution reaction of
ClCH2SiH3/ClCH2SiCl3 with AlCl3 as the catalyst. Although AlCl3
was reported can catalyze the redistribution reaction between
hydrosilane and chlorosilane at high temperature without solvent
[6a], no reaction was observed for the AlCl3 catalyzed ClCH2SiH3/
ClCH2SiCl3 system in tetrahydrofuran (THF) at room temperature
(Table 1, entry 1). The result may be due to that in THF, AlCl3 can-
not be well dissociated to produce enough chloride ion. To verify
the assumption, THF was replaced with 1,3-dimethyl-2-imidazo-
lidinone (DMI), which has a better ability to separate charges for
its higher dielectric constant [7] according to Coulomb’s law. As
expected, the redistribution reaction occurred quickly with two
hydrochlorosilanes formed in a total yield of 84% (Table 1, entry
2). The result verified presence of the possible Si-H/Si-Cl redistri-
bution reaction we assumed. Considering the better solubility of
lithium salts, we then used LiCl as the catalyst to investigate the
workable solvent for this redistribution system. It was found that
many solvents, including N, N’-1, 3-dimethylpropyleneurea
(DMPU), N-Methyl pyrrolidone (NMP), hexamethyl phosphoric tri-
amide (HMPA), tetrahydrofuran (THF), and diethylene glycol
dimethyl ether (diglyme) worked well for the redistribution reac-
tion between hydrosilane and chlorosilane (Table 1, entries 3–8).
Besides, the redistribution reaction did not take place in Bu2O or
Et2O (Table 1, entries 9 and 10), which may be due to the weaker
solvent polarity of them and the low solubility of LiCl in these sol-
vents [8a]. We also noticed that the reaction has lower conversion
efficiency in CH3CN, although it has higher polarity than diglyme.
The relatively low solubility of LiCl in CH3CN may be the reason
[8b]. These results indicated the appropriate polarity of solvent
and the solubility of catalyst in it are keys for the redistribution
reaction.
Table 1
Optimization of the reaction.a
Entry
Catalyst
Solvent
Time (h)
Products (yield)b
1
2
3
4
5
6
7
8
AlCl3
AlCl3
LiCl
LiCl
LiCl
LiCl
LiCl
LiCl
LiCl
LiCl
LiCl
NaCl
KCl
KF
KF
KBr
THF
DMI
DMI
20
3
3
3
3
3
3
3
3
20
20
10
10
0.5
10
10
10
0.5
3
No reaction
(1): 16%, (2): 68%
(1): 15%, (2): 70%
(1): 15%, (2): 68%
(1): 16%, (2): 61%
(1): 11%, (2): 70%
(1): 10%, (2): 69%
(1): 21%, (2): 18%
(1): 5%, (2): 8%
No reaction
DMPU
NMP
HMPA
diglyme
THF
CH3CN
Bu2O
Et2O
DMI
DMI
DMI
DMI
DMI
9
10
11
12
13
14
15
16
17
18
19
No reaction
(1): 16%, (2): 69%
(1): 16%, (2): 69%
(1): 28%, (2): 24%
(1): 15%, (2): 70%
(1): 15%, (2): 70%
(1): 14%, (2): 71%
(1): 16%, (2): 65%
(1): 14%, (2): 69%
KI
DMI
DMI
DMI
KF/18-crown-6
KF/18-crown-6
a
Reaction conditions: ClCH2SiH3 (0.005 mol), ClCH2SiCl3 (0.01 mol), catalyst
(3.0 mol/%), solvent (1 mL), room temperature.
To have an insight into the catalytic mechanism, we further
studied Si-H/Si-Cl redistribution reaction with PhSiH3/PhSiCl3 as
b
Yields were determined by 1H NMR.

Y. Chen et al. / Tetrahedron Letters 61 (2020) 152235
3
Table 2
Substrate scope of the Si-H/Si-Cl redistribution reaction.a
Entry
R4-xSiHx/R4-xSiClx
Ratio
Cat. (mol %)
T (h)
Products (yield)b
1
2
ClCH2SiH3/ClCH2SiCl3
ClCH2SiH3/ClCH2SiCl3
1:2
2:1
1 (3)
1 (3)
10
10
ClCH2SiHCl2: 71%, ClCH2SiH2Cl: 14%
ClCH2SiHCl2: 20%
ClCH2SiH2Cl: 65%
ClCH2SiMeHCl: 69% (56%c)
ClCH2SiMeHCl: 64%
Cl2CHSiMeHCl: 70% (60%c)
Cl2CHSiMeHCl: 65%
No reaction
3
4
5
6
7
8
9
ClCH2SiMeH2/ClCH2SiMeCl2
ClCH2SiMeH2/ClCH2SiMeCl2
Cl2CHSiMeH2/Cl2CHSiMeCl2
Cl2CHSiMeH2/Cl2CHSiMeCl2
Et2SiH2/Et2SiCl2
1:1
1:1
1:1
1:1
1:1
1:1
1:2
1 (2)
2 (2)
1 (2)
2 (2)
1 (4)
2 (4)
1 (3)
10
10
36
48
20
14
20
Et2SiH2/Et2SiCl2
PhSiH3/PhSiCl3
Et2SiHCl: 15%
PhSiHCl2: 63%
PhSiH2Cl: 11%
10
PhSiH3/PhSiCl3
2:1
1 (3)
20
PhSiHCl2: 18%
PhSiH2Cl: 44%
11
12
13
PhMeSiH2/PhMeSiCl2
Ph2SiH2/Ph2SiCl2
Ph2SiH2/Ph2SiCl2
1:1
1:1
1:1
1 (4)
1 (4)
2 (4)
20
48
14
PhMeSiHCl: 52%
Ph2SiHCl: 17%
Ph2SiHCl: 31%
a
Reaction conditions: [entry 3–8, 11–13] hydrosilane/chlorosilane, (0.01/0.01 mol); [entry 1, 6] hydrosilane/chlorosilane, (0.01/0.02 mol); [entry 2, 7] hydrosilane/
chlorosilane (0.02/0.01 mol), DMI (1 mL).
b
yields were determined by 1H NMR.
c
Isolated yield with larger scale. Reaction conditions: hydrosilane/chlorosilane (0.2/0.2 mol), DMI (10 mL), KF/18-C-6 (2 mol %), Room temperature.
Table 3
100
Control experiments of the Si-H/Si-Cl redistribution reaction.a
PhSiHCl
2
PhSiH2Cl
PhSiHCl + PhSiH Cl
2
2
80
60
40
20
0
Entry
Catalyst
Solvent
Time (h)
Products (yield)b
1
2
3
4
5
6
7
None
None
None
Li2CO3
TBAC
LiCl
THF
diglyme
DMI
DMI
DMI
6
6
6
6
6
6
6
No reaction
No reaction
(1): 7%, (2): 19%
(1): 50%, (2): 13%
(1): 51%, (2): 6%
(1): 60%, (2): 11%
(1): 54%, (2): 14%
DMI
DMI
LiH
a
Reaction conditions: PhSiH3 (0.005 mol), PhSiCl3 (0.01 mol), catalyst (3.0 mol/
%), solvent (1 mL), room temperature.
b
Yields were determined by 1H NMR.
the model substrate (Table 3). The solvents used herein are also
Lewis bases, which have been shown to activate the Si-H bond
[5c]. To prove the catalytic effect of metal chloride in the redistri-
bution reaction, we then compared the reaction of PhSiH3 and
PhSiCl3 in different solvents with and without LiCl. It was found
that the redistribution reaction slowly proceeded in DMI, but no
change was observed in THF or diglyme within experimental time
(Table 3, entries 1–3). The stronger Lewis basicity of DMI than that
of THF and diglyme [11] may account for the phenomenon. After
addition of LiCl, the reaction in DMI was obviously accelerated
(Table 3, entry 6), which clearly indicates the catalytic effect of LiCl.
During the Si-H/Si-Cl redistribution process, the proportion of
PhSiHCl2 increased quickly at the initial stage, then the increase
slowed down after 3 h. The proportion of PhSiH2Cl increased first,
and then decreased to about 11%, which may be due to the redis-
tribution of the formed PhSiH2Cl with the excess PhSiCl3 substrate
(Fig. 1).
0
5
10
15
20
Time (h)
Fig. 1. Products yields to time during the Si-H/Si-Cl redistribution reaction of
PhSiH3/PhSiCl3 (1:2) catalyzed by LiCl in DMI.
soluble metallic salt or non-metallic salt can also be effective cat-
alyst for the reaction. On the other hand, the result may prove that
both the Li+ and Cl- ion play an important role in the activation of
Si-H bond. The role Cl- plays in this process can be easily under-
stood by referring to the reported work about activation of Si-H
bond by Lewis bases [5c], i.e., the Si-H bond is activated through
the attack of Cl- at the silicon center to form a pentacoordinate
intermediate. In addition, the metal cation may act as the H- accep-
tor through the interaction with the activated Si-H bond, which
further promotes the dissociation of Si-H bond. Therefore, we pro-
posed a tentative mechanism for the Si-H/Si-Cl redistribution reac-
tion as depicted in Schemes 1 and 2. The Si-H bond of hydrosilane
is first activated through attack of Lewis base like Cl- or DMI at the
silicon center to form a pentacoordinate intermediate. Then the
activated Si-H bond of the intermediate breaks to form hydride
and the corresponding substituted product. The existence of Li+
For a better understanding of the role LiCl plays in this redistri-
bution process, we then examined the catalytic effect of Li2CO3 and
tetrabutylammonium chloride (TBAC) (Table 3, entries 4, 5). It was
found that both of them can catalyze the redistribution of PhSiH3
and PhSiCl3 in DMI successfully. The result indicates that the range
of catalyst is actually not limited to alkali metal halide salt, other

4
Y. Chen et al. / Tetrahedron Letters 61 (2020) 152235
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.tetlet.2020.152235.
References
Scheme 1. Plausible mechanism of DMI solvent catalytic Si-H/Si-Cl redistribution
process.
[1] (a) R. Drake, I. MacKinnon, R. Taylor, The Chemistry of Organic Silicon
Compounds, John Wiley & Sons Ltd, 2003, pp. 2217–2244;
(b) B. Arkles. In Kirk-Othmer Encyclopedia of Chemical Technology American
Cancer Society, 2000.;
(c) W. Xue, M.C. Kung, H.H. Kung, Chem Commun. (2005) 2164–2166;
(d) B. Marciniec. In Hydrosilylation:
A Comprehensive Review on Recent
Advances; B. Marciniec, Ed.; Springer, Netherlands: Dordrecht, 2009; pp 159–
189..
[2] (a) R.J.P. Corriu, C. Guerin. In Advances in Organometallic Chemistry; F.G.A.
Stone, R. West, Eds.; Academic Press, 1982; Vol. 20, pp 265–312.;
(b) L.N. Lewis, Lewis Nathan, J. Am. Chem. Soc. 108 (1986) 7228–7723.
[3] (a) Y. Furukawa, T. Yoneda, J. Polym. Sci. Part A 41 (2003) 2704–2714;
(b) B. Boutevin, F. Guida-Pietrasanta, A. Ratsimihety, J. Polym. Sci Part A 38
(2000) 3722–3728;
Scheme 2. Plausible mechanism of LiCl catalytic Si-H/Si-Cl redistribution process.
in the solution may accelerate this process. On the other hand, the
hydride produced in situ can reduce Si-Cl to Si-H bond again and
produce Cl-, which then participates in the next chlorination
process. The two processes occur simultaneously and drive the
redistribution reaction between hydrosilane and chlorosilane.
To verify the LiCl catalytic mechanism described in Scheme 2,
the redistribution reaction of PhSiH3/PhSiCl3 catalyzed by LiH
was carried out in DMI, which proceeded successfully as expected
(Table 3, entry 7). In addition, we noticed that various hydrides
have been reported to catalyze the Si-H/Si-C exchange reaction of
hydrosilane in different solvents, and a similar mechanism involv-
ing hypervalent silicon hydrides intermediate was proposed [12]. A
fast racemization of the optically active 1-Np-PhMeSiH catalyzed
by hydrides was also observed, which can be rationalized in terms
of the formation of a pentacoordinate hydridoorganosilyl anion
[12b]. Considering chlorine on silicon is a much better leaving
group than alkyl or aryl substituent [13], the Si-H bond may redis-
tribute with Si-Cl bond without rupturing the Si-C bond through
similar ligand exchange process. Therefore, we think the mecha-
nism study of Si-H/Si-C redistribution reaction catalyzed by
hydrides may be a good reference for understanding the mecha-
nism we proposed herein to explain the Si-H/Si-Cl redistribution
reaction.
(c) A. Iraqi, S. Seth, C.A. Vincent, D.J. Cole-Hamilton, M.D. Watkinson, I.M.
Graham, D. Jeffrey, J. Mater. Chem. 2 (1992) 1057–1064.
[4] (a) T. Hiiro, H. Sakurai, F. Kondo. United States, US4115426A 1978.;
(b) A. Glüer, J.I. Schweizer, U.S. Karaca, C. Würtele, M. Diefenbach, M.C.
Holthausen, S. Schneider, Inorg. Chem. 57 (2018) 13822–13828;
(c) T. Beppu, K. Sakamoto, Y. Nakajima, K. Matsumoto, K. Sato, S. Shimada, J.
Organometal. Chem. 869 (2018) 75–80.
[5] (a) A. Kunai, T. Kawakami, E. Toyoda, M. Ishikawa, Organometallics 11 (1992)
2708–2711;
(b) K. Chulsky, R. Dobrovetsky, Angew. Chem. Int. Ed. 56 (2017) 4744–4748;
(c) A.G. Sturm, J.I. Schweizer, L. Meyer, T. Santowski, N. Auner, M.C.
Holthausen, Chem. – A, Eur. J. 24 (2018) 17796–17801;
ˇ
ˇ
(d) A. Šimarek, M. Lamac, M. Horácek, J. Pinkas, Appl. Organometal. Chem. 32
(2018) e4442;
(e) R. Savela, W. Zawartka, R. Leino, Organometallics 31 (2012) 3199–3206.
[6] (a) F.C. Whitmore, E.W. Pietrusza, L.H. Sommer, J Am Chem Soc. 69 (1947)
2108–2110;
(b) A. Benouargha, D. Boulahia, B. Boutevin, G. Caporiccio, F. Guida-
pietrasanta, A. Ratsimihety, Phosphorus Sulfur Silicon Related Elem. 113
(1996) 79–87;
(c) I.N. Jung, B.R. Yoo, J.S. Han, W.-C. Lim. United States, US5965762A 1999.;
(d) K. Wakabayashi, H. Tanaka. United States, US20110207886A1 2011..
[7] (a) D.J. Metz, A. Glines, J Phys Chem. 71 (1967) 1158;
(b) Ch. Wohlfarth. In Supplement to IV/6; M.D. Lechner, Ed.; Springer, Berlin
Heidelberg: Berlin, Heidelberg, 2008; Vol. 17, pp 295–295..
[8] (a) H.C. Brown, Choi Y. Moon, S. Narasimhan, Inorg. Chem. 21 (1982) 3657–
3661;
(b) N. Xin, Y. Sun, M. He, C.J. Radke, J.M. Prausnitz, Fluid Phase Equilibria 461
(2018) 1–7.
[9] (a) A.J. Parker, Q. Rev. Chem. Soc. 16 (1962) 163–187;
(b) Y. Marcus, Ion Solvation, Wiley, 1985.
[10] (a) Chuit Claude, R.J.P. Corriu, Reye Catherine, Young J. Colin, Chem Rev. 93
(1993) 1371–1448;
(b) S.E. Johnson, R.O. Day, R.R. Holmes, Inorg Chem. 28 (1989) 3182–3189.
[11] J.-F. Gal, In Lewis Base Catalysis in Organic Synthesis John Wiley & Sons, Ltd,
2016; pp 55–84.
In summary, we have established a metal halide catalyzed Si-H/
Si-Cl redistribution system. Various simple and common alkali
metal halides can be utilized as the catalyst. The redistribution
reaction may take place through Lewis base participated silicon
pentacoordinate intermediate. The very mild reaction conditions
and the economically practical strategy are the advantages the
redistribution system possesses, compared with the Si-H/Si-Cl
redistribution system reported previously. Further improvement
of the redistribution system is pursued in our laboratory.
[12] (a) B. Becker, R.J.P. Corriu, C. Guérin, B.J.L. Henner, J. Organometal Chem 369
(1989) 147–154;
(b) J.L. Brefort, R. Corriu, C. Guérin, B. Henner, J. Organometal. Chem. 370
(1989) 9–15.
[13] D.R. Weyenberg, L.G. Mahone, W.H. Atwell, Ann. NY Acad. Sci. 159 (1969) 38–
55.