Trimethylsilyl Pseudohalide Adducts of GaCl3 and B(C6F5)3

Article abstract of DOI:10.1002/ejic.202100237

Me₃Si?X (X=CN, N₃, OCN, and SCN) was treated with the Lewis acids GaCl₃ and B(C₆F₅)₃ in toluene yielding the desired adducts Me₃Si?X→GaCl₃ and Me₃Si?X→B(C₆F₅)₃. All synthesized adducts were isolated and completely characterized including single crystal structure elucidations. The different structures, thermodynamics of formation and charge transfer effects are discussed on the basis of experimental and theoretical data.

Full text of DOI:10.1002/ejic.202100237

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Trimethylsilyl Pseudohalide Adducts of GaCl3 and B(C6F5)3
Kevin Bläsing,[a] Jonas Bresien,[a] Steffen Maurer,[a] Axel Schulz,*[a, b] and Alexander Villinger[a]
Me3SiÀ X (X=CN, N3, OCN, and SCN) was treated with the Lewis
acids GaCl3 and B(C6F5)3 in toluene yielding the desired adducts
Me3SiÀ X!GaCl3 and Me3SiÀ X!B(C6F5)3. All synthesized adducts
were isolated and completely characterized including single
crystal structure elucidations. The different structures, thermo-
dynamics of formation and charge transfer effects are discussed
on the basis of experimental and theoretical data.
Introduction
Adducts, also known as donor-acceptor complexes, are formed
when a Lewis acid (electron acceptor, LA) forms a bond with a
Lewis base (electron donator, LB).[1,2] Such donor-acceptor
molecular complexes (LB!LA) can either be formed by a σ- or
π-bond,[3–8] which is often called a dative bond.[9] Lewis acids
and bases as well as their LB!LA complexes play a vital role in
Scheme 1. Stabilization of labile pseudo halide acids by adduct
formation.[15,16,54]
catalysis,[10–12] FLP chemistry,[13] chemical vapor decompo- Results and Discussion
sition,[11] stabilization of labile Lewis acidic or basic
fragments,[14–16] structural chemistry[17–19] as well as formation of
weakly coordinating anions.[20–23] Amongst many other Lewis
Synthesis
[27–33]
[34–40]
acids,[10–13,24–26] GaCl3
and B(C6F5)3
have been used in
We started this project with the synthesis of the starting
materials Me3SiÀ X and B(C6F5)3 (see Supporting Information).
While Me3SiCN was purchased and distilled prior to use, all
other Me3SiÀ X compounds were synthesized utilizing modified
literature procedures.[14,59]
main group chemistry in the last decades. In recent years, we
have frequently used GaCl3 as Lewis acid for the generation of
reactive cations by chloride abstraction[41–49] and in GaCl3-
assisted [3+2] cycloaddition reactions yielding phosphorus-
nitrogen heterocycles.[50–53] B(C6F5)3-adducts have been utilized
in our group to stabilize highly labile pseudohalide entities,
such as a HCN dimer (Scheme 1A), HN3 (Scheme 1B) and HNSO
(Scheme 1C).[15,16,54]
B(C6F5)3 adducts
As [Me3Si]+ can be considered a large proton,[55–57] we were
interested in synthesizing GaCl3 and B(C6F5)3 adducts of Me3SiÀ X
(X=pseudohalogen) to study their structure, connectivity and
bonding depending on the used Lewis acid and the pseudohal-
ogen. There are already two reports describing the synthesis
and structure of Me3SiÀ N3!GaCl3 and Me3SiÀ CN!GaCl3.[32,58]
Here we report on the synthesis and structure of the hitherto
unknown Me3SiÀ X!LA adducts (LA=GaCl3 and B(C6F5)3; X=CN,
N3, OCN, and SCN).
Except for X=NCO, synthesis of B(C6F5)3 adducts Me3SiÀ X!
B(C6F5)3 was achieved by addition of pure liquid Me3SiÀ X to a
degassed suspension of B(C6F5)3 in toluene (X=CN, N3) or by
using an excess of Me3SiÀ X without further solvent (X=NCS,
Scheme 2). The suspensions at the beginning became clear
after gentle heating. Colorless single crystals suitable for X-ray
structure elucidation were grown by cooling utilizing different
procedures (See Supporting Information). The yields range
between 92 and 22% [92% (CN), 71% (N3), 22% (NCS)]. All
B(C6F5)3 adducts are moisture sensitive and melt between 108
°
(X=NCS) and 155 C (CN) without decomposition. Even the
°
Me3SiÀ N3 adduct melts without decomposition at 120 C and
[a] Dr. K. Bläsing, Dr. J. Bresien, S. Maurer, Prof. Dr. A. Schulz, Dr. A. Villinger
Anorganische Chemie, Institut für Chemie
Universität Rostock
A.-Einstein-Str. 3a, 18059 Rostock, Germany
E-mail: axel.schulz@uni-rostock.de
[b] Prof. Dr. A. Schulz
°
decomposes above 189 C. Notably, it was impossible to obtain
the adduct Me3SÀ NCO!B(C6F5)3 since there was no reaction
between the borane and Me3SiÀ NCO according to solution
NMR data in accord with computational results (see below).
The attempted formation of diadducts of the type Me2Si-
[X!B(C6F5)3]2 also failed, except for X=CN. For this purpose,
Me2SiX2 was reacted with two equivalents of the borane in
toluene, which should lead to the formation of the diadduct if
possible. A yellow solution was obtained, which, however, only
led to crystallization of the diadduct in the case of X=CN (a few
crystals) when such a solution was cooled down in the
Materialdesign
Leibniz-Institut für Katalyse an der Universität Rostock
A.-Einstein-Str. 29a, 18059 Rostock, Germany
Supporting information for this article is available on the WWW under
https://doi.org/10.1002/ejic.202100237
© 2021 The Authors. European Journal of Inorganic Chemistry published by
Wiley-VCH GmbH. This is an open access article under the terms of the
Creative Commons Attribution License, which permits use, distribution and
reproduction in any medium, provided the original work is properly cited.
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Scheme 2. Synthesis of Me3SiÀ X!B(C6F5)3 adducts (X=CN, N3, NCO, and
NCS).
Scheme 3. Synthesis of Me3SiÀ X!GaCl3 adducts (X=CN, N3, NCO, and NCS).
Table 1. Selected NMR data of the starting materials and all isolated
adducts. Assignment of the isomers was carried out on the basis of
computations in combination with the X-ray structure studies (See
Figures 1–3, Table S12).
of Me3SiÀ X, the solution became colorless within a few seconds
and colorless single crystals suitable for X-ray structure
elucidation were grown by cooling the solution (see Supporting
Information). The crystals were rather unstable and often
decomposed within a few minutes at ambient temperatures, a
feature that has already been addressed by Kouvetakis et al. for
X=N3. Here, decomposition starts with the elimination of
Me3SiÀ Cl along with the formation of Cl2GaÀ X.[32] Kouvetakis
et al. prepared Me3SiN3!GaCl3 by adding Me3SiN3 to a frozen
Compound
1H
11B
14N{1H}
29Si
B(C6F5)3
Me2Si(CN)2
Me3SiCN
Me3SiNC!B(C6F5)3
Me3SiNC!GaCl3
Me3SiN3
59.8
–
–
0.65
0.98
0.56
À 0.28
0.29
À 79.0
À 88.0
À 36.6
À 11.2
25.4
30.2
16.3
À 22.0
À 192.9
a
–
À 321.5α
À 145.4β
À 209.3γ
À 323.3α
À 172.1β
°
solution of GaCl3 at À 196 C, while we found that it is not
Me3SiN3!B(C6F5)3 (1,1 isomer)
0.34
20.7
32.8
necessary to work at very low temperatures. We added Me3SiN3
À 143.5γ
°
at À 40 C and allowed the solution to warm up to ambient
b
Me3SiN3!GaCl3 (1,1 isomer)
Me3SiNCO
Me2Si(NCO)2
0.01
0.28
0.31
–
–
–
–
–
–
38.7
4.3
À 18.2
21.4
6.0
À 22.3
20.7
22.8
temperatures. Crystals were obtained by slowly cooling down
À 344.2
À 344.2
À 325.6
À 261.2
À 268.8
-
°
to À 20 C overnight.
Also, 29Si NMR spectroscopy can be used to follow adduct
formation in solution for both GaCl3 as well as B(C6F5)3 adduct
formation (Table 1, Δ[δ29Si]sm-GaCl3-adduct =À 41.4 (X=CN), À 22.4
(N3), À 17.1 (NCO), and À 16.8 ppm (NCS)). However, in case of
the GaCl3 adducts this shift is slightly larger compared to those
upon B(C6F5)3 adduct formation (cf. Δ[δ29Si]sm-B(C6F5)3-adduct =À 36.6
(X=CN), À 16.5 (N3), and À 14.7 ppm (NCS)).
Me3SiNCO!GaCl3 (1,1 isomer)
À 0.17
Me3SiNCS
0.31
Me2Si(NCS)2
0.53
0.60
À 0.09
Me3SiSCN!B(C6F5)3 (1,3 isomer)
À 10.7
Me3SiNCS!GaCl3 (1,3 isomer)
–
À 223.1
[a] Values not given in ref. [58] [b] Not reported in ref. [32]
refrigerator. For X=OCN and SCN, however, no reaction was
observed according to NMR data.
Structure
Especially, 11B NMR studies are particularly well suited to
visualize adduct formation in solution, since there is a very large
shift in the 11B resonance of the B(C6F5)3 moiety when the
adduct is formed (Table 1, Δ[δ11B]sm-adduct =81.8 (X=CN), 80.5
(N3), and 70.5 ppm (NCS); sm=starting material).
X-ray quality crystals were selected in Fomblin YR-1800
perfluoroether (Alfa Aesar) under a stream of cooled nitrogen.
The samples were cooled to 123(2) K during measurement. The
single crystal X-ray structures were determined of the mono-
adduct Me3SiÀ X!B(C6F5)3, X=CN, N3, SCN and diadduct Me2Si-
[CN!B(C6F5)3]2 as well as Me3SiX!GaCl3, X=N3, OCN, SCN. It
should be noted that the structures of Me3SiÀ N3!GaCl3 and
Me3SiÀ CN!GaCl3 have already been published but their data
will be used for comparison.[32,58] Since our structural data of
Me3SiÀ N3!GaCl3 are slightly different to the published ones
but with better R values, we will use our data set in the
discussion. Selected structural data are listed in Table 1.
GaCl3 adducts
To synthesize GaCl3 adducts of Me3SiÀ X, gallium trichloride was
either dissolved in CH2Cl2 (X=CN, SCN), toluene (X=N3) or in an
excess of pseudohalogenotrimethylsilane (X=NCO) resulting
always in a slightly yellow solution (Scheme 3). Upon addition
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While mono- as well as the diadducts of the CN species are
always 1,2-isomers (Figure 1) with the N atom attached to the Si
atom, the azide adducts feature always the 1,1-isomer (Fig-
ure 2). For X=OCN, also the 1,1-isomer with the N attached to
the Si/Ga was found for the GaCl3 adduct. Only the 1,3-isomers
were observed for X=SCN both for the B(C6F5)3 and GaCl3
adduct, however, with the Ga attached to the sulfur atom and
the borane linked to the nitrogen atom (Figure 3). See Table 2
for selected structural data.
Figure 3. ORTEP representations of Me3Si(NCO)!GaCl3 (1,1 isomer, top);
bottom: Me3SiNCS!B(C6F5)3 (1,3 isomer) and Me3SiNCS!GaCl3 (1,3 isomer)
in the crystal (selected structural data are listed in Table 2). Color code: B
brown, C gray, Si violet, F light blue, N blue, S yellow, Ga turquoise, Cl, green
and H white.
A closer look at the structural data shows that the BÀ C and
BÀ N donor-acceptor bonds (d(BÀ C)=1.610–1.617, d(BÀ N)=
1.587–1.648 Å) are slightly longer than a classical BÀ C and BÀ N
covalent bond (cf. Σrcov(BÀ C)=1.60, Σrcov(BÀ C)=1.56 Å).[60] The
same applies to the GaÀ C and GÀ N bonds (d(GaÀ C)=2.029(4),
d(GaÀ N)=1.999(2), Σrcov(GaÀ C)=1.99, Σrcov(GaÀ N)=1.95 Å).[60]
Interestingly, the BÀ N bond length in the 1,3-isomer of
Me3SiÀ SCN!B(C6F5)3 is significantly shorter (1.587(2) Å) than
that in the 1,1-isomer of Me3SiÀ N3!B(C6F5)3 (1.648(2) Å).
Furthermore, the CN bonds in all three cyanido-adducts are still
in the range of a typical CN triple bond (1.141–1.155 Å,
Σrcov(C�N)=1.14 Å), while in the OCN adduct these are
significantly longer with 1.229(4) Å and are in the range of CN
double bond (Σrcov(C=N)=1.29 Å). In contrast the CÀ O bond is
rather short with 1.153(4) Å (cf. Σrcov(C=O)=1.24 Å, Σrcov(C�O)=
1.13 Å).[60]
In the azides, it is noticeable that there are two clearly
distinguishable NÀ N bonds. A rather long one was found for
the N atom that forms the dative bond with the respective
Lewis acid (d(NαÀ Nβ): 1.259(1)–1.261(2) Å, cf. (Σrcov(N=N)=
1.20 Å), while the terminal N atom has a significantly shorter
NβÀ Nγ bond within the N3 unit with 1.116(2)–1.117(2) Å (Σrcov-
(N�N)=1.08 Å), which is close to the distance for a triple bond.
Hence, an N2 molecule is pre-formed in the N3 adducts.
Figure 1. ORTEP representations of Me3SiNC!B(C6F5)3 (1,2 isomer) and
Me2Si[NC!B(C6F5)3]2 in the crystal (selected structural data are listed in
Table 2). Color code: B brown, C gray, Si violet, F light blue, N blue and H
white.
The rhodanide complexes show a clear difference in the
°
angle to the Lewis acid (a(CÀ NÀ B)=176.5(2) vs. a(CÀ SÀ Ga)=
°
97.7(1) ), which is due to the fact that in the GaCl3 adduct, the
GaCl3 coordinates to the heavy sulfur atom, just as in the
analogous OCN adduct (here to the O atom – the lighter
chalcogen), whereas in the borane adduct, the boron atom is
linked to the nitrogen. That is, both adducts are different in
terms of coordination to the rhodanide moiety, since in the
borane adduct there is formally a trimethylsilyl thiocyanate,
while in the GaCl3 adduct there is an isothiocyanate. Obviously,
the larger borane prefers the N atom, which leads to a
minimization of the Pauli repulsion in the molecule, which is
Figure 2. ORTEP representation of Me3SiN3!B(C6F5)3 (1,1 isomer) and
Me3SiN3!GaCl3 (1,1 isomer) in the crystal (selected structural data are listed
in Table 2). Color code: B brown, C gray, Si violet, F light blue, N blue, Ga
turquoise, Cl, green and H white.
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[a]
°
Table 2. Selected experimental bond lengths (Å) and angles ( ).
Compound
SiÀ X
XÀ Y
YÀ Z
X/ZÀ LA
XÀ YÀ Z
SiÀ XÀ Y
YÀ X/ZÀ LA
Me3SiNC!B(C6F5)3
1.822(2)
1.858(3)
1.815(2)
1.874(2)
1.854(2)
–
1.861(3)
2.253(1)
1.819(2)
1.148(2)
1.141(4)
1.155(3)
1.259(1)
1.261(2)
–
1.229(4)
1.663(2)
1.149(2)
–
–
–
1.617(2)
2.029(4)
1.610(3)
1.648(2)
1.999(2)
–
2.019(2)
1.587(2)
2.371(1)
–
–
–
165.9(2)
180.0
168.4(2)
116.65(9)
116.1(2)
–
119.6(2)
97.8(1)
179.1(2)
177.8(2)
180.0
176.4(2)
129.20(7)
115.2(2)
–
114.5(2)
176.5(2)
97.7(1)
b
Me3SiNC!GaCl3
Me2Si(NC!B(C6F5)3)2
Me3SiN3!B(C6F5)3 (1,1 isomer)
Me3SiN3!GaCl3 (1,1 isomer)
Me3SiNCO!B(C6F5)3 not formed
Me3SiNCO!GaCl3 (1,1 isomer)
Me3SiSCN!B(C6F5)3 (1,3 isomer)
Me3SiNCS!GaCl3 (1,3 isomer)
1.117(2)
1.116(2)
–
1.153(4)
1.144(2)
1.644(2)
179.6(1)
178.6(2)
–
179.6(4)
177.8(2)
176.5(2)
[a] X, Y, Z correspond to the α, β, γ atoms of the pseudohalogen; LA=Lewis acid, depending on the connectivity (1,1 or 1,3 isomer). [b] Taken from ref. [58]
consistent with our quantum chemical calculations (see below).
Moreover, boron as element of the 2nd period prefers bonding
to the N atom, also an element of the 2nd period, while the Ga
atom as element of the 4th period forms the bond to the S
atom.
in Table 3 is that molecular structures in the solid state always
correspond to the thermodynamically most stable isomer. For
example, both Me3SiÀ NC!LA adducts are favored over the
Me3SiÀ CN!LA complexes (B(C6F5)3: 6.3, GaCl3: 1.93 kcalmolÀ 1).
In agreement with experiment, no stable B(C6F5)3 adduct with
Me3SiÀ NCO/Me3SiÀ OCN was found as all Gibbs energies are
positive. In contrast, the 1,1-GaCl3 adduct of Me3SiÀ NCO is
À 1
°
Thermodynamics
formed with an energy gain of ΔrG =À 9.41 kcalmol , whereas
all Me3SiÀ OCN adducts are thermodynamically unstable with
respect to dissociation. The 1,3-isomer of the Me3SiÀ NCO
adduct is 2.02 kcalmolÀ 1 less stable than the experimentally
found 1,1 adduct.
To shed some light into the formation of the different possible
adduct isomers, quantum chemical computations have been
performed at the DLPNO-CCSD(T)/def2-TZVPP//PBE0-D3BJ/def2-
TZVP level of theory. Selected structural parameters are listed in
Tables S13–S14 and the adduct formation energies in Table 3.
The most essential statement of the thermodynamic calcula-
tions in relation to the adduct formation reaction as described
For the rhodanide adducts, the situation is different. While
the 1,3-GaCl3 adduct of Me3SiÀ NCS is the most stable complex
with À 7.66 kcalmolÀ 1, for the B(C6F5)3 adduct, all complexes
were computed to be thermodynamically unstable with respect
to adduct dissociation.
However, since it was possible to isolate 1,3-Me3SiÀ SCN!
B(C6F5)3, it can be assumed that solid state effects such as
intermolecular dipole-dipole interactions result in the formation
Table 3. Reactions energies (DLPNO-CCSD(T)/def2-TZVPP//PBE0-D3BJ/
def2-TZVP, in kcal·molÀ 1). Formation reaction of Me3SiXÀ LS: Me3SiÀ X+
LA!Me3SiX!LA.
of thermodynamically stable molecules in the solid. Moreover,
Me3SiX!LA
ΔEtot
ΔRH
ΔRG
°
°
À 1
°
the Gibbs energy, ΔrG =3.48 kcalmol , for the formation is
Me3SiCN!B(C6F5)3
À 22.02
À 28.57
À 25.32
À 25.36
À 21.30
À 10.63
À 27.43
À 16.95
À 12.21
À 9.07
À 19.12
À 25.62
À 24.45
À 23.96
À 18.61
À 7.96
À 26.11
À 15.50
À 8.44
À 5.29
13.72
À 10.09
À 16.39
À 11.94
À 13.87
À 5.96
2.85
rather small so this can easily be compensated by intermolecu-
lar attractive effects. Experimentally, it was found that the
isolated crystals are very unstable at ambient temperatures.
Additionally, since we started from the Me3SiÀ NCS in the
experiment, an isomerization process must have occurred,
which afforded finally Me3SiÀ SCN!B(C6F5)3. Again, in agree-
ment with experiment, all azide adducts found experimentally
are those computed to be the most thermodynamically stable
isomers. That is, the 1,1 isomers that have a preformed N2 unit,
are 8.8 (B(C6F5)3) and 9.92 kcalmolÀ 1 (GaCl3) more stable than
the 1,3 isomers. Finally, a word about charge transfer (see
Table S15). It was found that the stronger Lewis acid, B(C6F5)3, in
the corresponding borane adducts receives about 0.35–0.58e
from the Me3SiX molecule, while GaCl3 receives only about half
of that (0.17–0.29e).
Me3SiNC!B(C6F5)3
Me3SiCN!GaCl3
Me3SiNC!GaCl3
(1,1)Me3SiN3!B(C6F5)3
(1,3)Me3SiN3!B(C6F5)3
(1,1)Me3SiN3!GaCl3
(1,3)Me3SiN3!GaCl3
(1,1)Me3SiNCO!B(C6F5)3
(1,3)Me3SiNCO!B(C6F5)3
(1,1)Me3SiOCN!B(C6F5)3
(1,3)Me3SiOCN!B(C6F5)3
(1,1)Me3SiNCO!GaCl3
(1,3)Me3SiNCO!GaCl3
(1,1)Me3SiOCN!GaCl3
(1,3)Me3SiOCN!GaCl3
(1,1)Me3SiNCS!B(C6F5)3
À 13.62
À 3.71
1.43
1.15
20.09
5.34
À 9.41
À 7.39
16.96
0.65
4.13
1.61
[a]
[a]
10.35
À 5.96
À 2.33
À 19.15
À 15.81
7.72
À 8.23
À 8.26
À 7.65
13.29
À 21.59
À 18.21
5.81
À 10.46
À 10.76
À 10.22
11.30
[a]
(1,3)Me3SiNCS!B(C6F5)3
(1,1)Me3SiSCN!B(C6F5)3
(1,3)Me3SiSCN!B(C6F5)3
(1,1)Me3SiNCS!GaCl3
(1,3)Me3SiNCS!GaCl3
(1,1)Me3SiSCN!GaCl3
(1,3)Me3SiSCN!GaCl3
24.04
3.48
À 5.94
À 7.66
12.37
À 0.77
À 9.41
À 6.93
À 17.96
À 18.66
1.13
À 19.15
À 19.90
0.31
Conclusion
À 12.81
À 11.79
[a] No stable adduct was found, only separated weakly interacting Lewis-
acid Lewis-base pairs with a distance larger than the sum of the van-der-
Waals radii.
In conclusion, we present a series of new Me3SiÀ X!LA adducts
(X=CN, N3, OCN, SCN; LA=B(C6F5)3, GaCl3). We discuss exper-
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solved by iterative methods (SHELXT)[61] and refined by full-matrix
imentally as well as theoretically the influence of the Lewis acid
strength and the bulkiness on the formation of the different
isomers. While for X=CN both Lewis acids form the 1,2-
Me3SiÀ NC!LA adduct, for the azide only the 1,1-isomers were
found to be the most favored isomers. In the case of the
cyanate species, it was only possible to isolate the GaCl3 adduct
as 1,1-Me3SiÀ NCO adduct, while it was impossible to produce
the analogous borane adduct, in accord with theory, which
predicted an endergonic process. The reaction of the heavier
congener, the rhodanide, Me3SiÀ NCS with both Lewis acid led
to different products: While both Lewis acids form an 1,3
isomer, the connectivity, however, was different. In the case of
the GaCl3 complex, Me3SiÀ NCS!GaCl3 was formed, whereas
with B(C6F5)3 the formation of Me3À SCN!B(C6F5)3 was observed.
least squares procedures (SHELXL).[62] Semi-empirical absorption
corrections were applied (SADABS).[63] All non-hydrogen atoms
were refined anisotropically and hydrogen atoms were included in
the refinement at calculated positions using a riding model.
Syntheses of adduct complexes
Me3SiNCÀ B(C6F5)3
To a degassed suspension of tris(pentafluorophenyl)borane B(C6F5)3
(221 mg, 0.43 mmol) in toluene (1.5 mL) cyanotrimethylsilane
Me3SiCN (54 mg, 0.54 mmol, ~72 μL) was added via μL-syringe. The
suspension became clear within a few seconds and after a few
more seconds a precipitate was observed. The precipitate was
°
dissolved by heating the solution to 60 C (oil bath). Colorless single
crystals suitable for X-ray structure elucidation were grown by
°
cooling the solution overnight to À 20 C (refrigerator with
Experimental Section
isopropanol bath). The supernatant is removed by syringe and
discarded. The remaining crystals are dried (1·10À 3 mbar) at 60 C
°
Caution! Me3SiÀ X (X=CN, N3) is highly toxic! Appropriate safety
precautions (e.g. HCN detector, gas mask, low temperature) should
be taken. Experimental spectra and additional crystal structure
representations can be found in the Supporting Information.
for 2 hours, yielding 241 mg (0.39 mmol, 92%) of isocyanotrimeth-
ylsilane tris(pentafluorophenyl)borane adduct [Me3SiNCÀ B(C6F5)3].
C22H9BF15NSi (611.19 g·molÀ 1): mp. 155 C, >300 C (dec.). EA calc.
°
°
1
(found), %: C, 43.23 (43.73); H, 1.48 (1.51); N, 2.29 (2.41). H NMR
General Information: All manipulations were carried out in oxygen-
and moisture-free conditions in an argon atmosphere using
standard Schlenk or dry-box techniques if not mentioned other-
wise.
1
1
13
°
(25 C, CD2Cl2, 300.13 MHz): δ=0.56 (s, 9H, CH3, J( H- C)=123 Hz,
2J(1H-29Si)=7.4 Hz). B NMR (25 C, CD2Cl2, 96.29 MHz): δ=À 22.0
11
°
13
1
°
(br, NB(C6F5)3, Δν1/2 =75 Hz). C{ H} NMR (25 C, CD2Cl2, 75.47 MHz):
δ=À 0.9 (s, SiCH3, 1J(13CÀ Si)=60 Hz), 114.5 (br, ipso-C6F5), 137.9
29
(dm, m-CF, 1J(13CÀ F)=249 Hz), 141.0 (dm, p-CF, 1J(13CÀ F)=
19
19
NMR spectra were obtained on a Bruker AVANCE 250, 300 or
251 Hz), 145.1 (br, CN), 148.8 (dm, o-CF, 1J(13CÀ F)=245 Hz). 14N{1H}
19
500 MHz spectrometer and were referenced internally to the
deuterated solvent (13C{1H}: CD2Cl2 δref =53.84 ppm, CD3CN δref
=
°
NMR (25 C, CD2Cl2, 36.14 MHz): δ=À 192.9 (br, SiÀ NC, Δν1/2
=
19
1
°
430 Hz). F{ H} NMR (25 C, CD2Cl2, 282.40 MHz): δ=À 162.2 (m, 6F,
1.3 ppm, C6D5CD3 δref =20.43 ppm), to protic impurities in the
m-CF, 1J(19FÀ C)=249 Hz), À 157.3 (m, 3F, p-CF, 1J(19FÀ C)=251 Hz),
13
13
deuterated solvent (1H: CHDCl2 δref =5.32 ppm, CHD2CN δref
=
À 133.3 (m, 6F, o-CF, 1J(19FÀ C)=245 Hz). Si INEPT NMR (25 C,
13
29
1.93 ppm, C6D5CHD2 δref =2.08 ppm) or externally (11B: BF3 ·EtO2
δref =0 ppm, 14N{1H}: CH3NO2 δref =0 ppm, 15N: CH3NO2 δref =0 ppm,
°
CD2Cl2, 59.63 MHz): δ=25.4 (dec, SiCH3, 2J(29SiÀ H)=7.4 Hz). IR (ATR,
1
32 Scans, 25 C, cmÀ 1)*: 2254 (m), 1645 (m), 1516 (s), 1460 (s), 1381
17O: H2O δref =0 ppm, 19F{1H}: CFCl3 δref =0 ppm, 29Si: Si(CH3)4 δref
=
°
(m), 1286 (m), 1263 (m), 1099 (s), 1086 (m), 979 (s), 970 (s), 922 (m),
901 (m), 864 (s), 843 (s), 808 (s), 773 (m), 766 (m), 750 (m), 731 (m),
689 (m), 681 (s), 644 (m), 635 (m), 613 (m), 584 (w), 544 (m). Raman
0 ppm). All measurements were carried out at ambient temperature
1
unless stated otherwise. 15N NMR shifts were derived from H-15N
HMBC NMR spectra.
(633 nm, 8 mW, 15 s, 20 acc., 25 C, cmÀ 1): 2975 (1), 2914 (2), 2254
°
Raman spectra of crystalline samples were recorded using a
LabRAM HR 800 Horiba Jobin YVON Raman spectrometer equipped
with an Olympus BX41 microscope with variable lenses. The
samples were excited by a red laser (633 nm, 17 mW, air-cooled
HeNe laser) or a green laser (532 nm, 50 mW, air-cooled, frequency-
doubled Nd:YAG solid-state laser). All measurements were carried
out at ambient temperature, if not stated otherwise. For some
crystalline samples, a Linkam THMS600 Temperature Controlled
stage was used to cool the substances during measurement.
(10), 1645 (2), 1392 (1), 1380 (1), 808 (1), 776 (1), 764 (1), 749 (1),
688 (1), 645 (3), 634 (1),628 (2), 587 (3), 582 (2), 578 (3), 544 (2), 488
(5), 457 (1), 445 (2), 392 (3),378 (1),372 (1), 355 (1), 345 (1), 283 (1),
263 (1), 241 (1), 230 (1), 216 (1). MS (CI+, m/z (%)): 73 (19) [Me3Si]+,
100 (100) [Me3SiCNH]+, 172 (91) [Me3SiÀ NCÀ SiMe3]+, 444 (42)
[Me3SiÀ NCÀ B(C6F5)2]+, 611 (65) [Me3SiÀ NCÀ B(C6F5)3]+.
Me3SiNCÀ GaCl3
Elemental analyses were obtained using an Elementar vario Micro
cube CHNS analyzer.
Gallium trichloride GaCl3 (182 mg, 1.03 mmol) was dissolved in
CH2Cl2 (2 mL) resulting in a slightly yellow solution. The solution
became colorless within a few seconds by adding cyanotrimeth-
Melting points (uncorrected) were determined using a Stanford
°
ylsilane Me3SiCN (103 mg, 1.04 mmol) at À 20 C (isopropanol bath).
À 1
°
Research Systems EZ Melt at a heating rate of 5 C·min
.
Colorless single crystals suitable for X-ray structure elucidation were
DSC analyses were carried out at a heating rate of 5 C·minÀ 1 using
°
°
grown by cooling the solution overnight to À 80 C. The crystals
were identified as Me3SiCNÀ GaCl3 adduct. The supernatant is
a Mettler-Toledo DSC 823e.
removed by syringe and discarded. The remaining crystals are dried
Mass spectra were recorded on a Thermo Electron MAT 95-XP
sector field mass spectrometer using crystalline samples.
(1·10À 3 mbar) at À 20 C for 20 minutes. The crystals were rather
°
unstable and decomposed within a few minutes at ambient
temperatures.
X-ray Structure Determination: X-ray quality crystals of all com-
pounds were selected in Kel-F-oil (Riedel de Haen) at ambient
temperatures. Single crystals were measured on a Bruker D8 Quest
or a Bruker Apex Kappa II CCD diffractometer using graphite-
monochromated Mo Kα radiation (λ=0.71073). The structures were
C4H9SiNGaCl3 (275.29 g·molÀ 1): 1H NMR (25 C, toluene-d8,
°
29
°
300.13 MHz): δ=À 0.28 (s), 0.21 (s). Si INEPT NMR (25 C, toluene-
2
1
d8, 59.63 MHz): δ=30.2 (dec, SiCH3, J(29SiÀ H)=6.5 Hz). A full set of
analytical data could be found in the literature.[58]
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5
© 2021 The Authors. European Journal of Inorganic Chemistry published
by Wiley-VCH GmbH
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These are not the final page numbers!

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doi.org/10.1002/ejic.202100237
Me3SiNCOÀ GaCl3 adduct (1,1 isomer). The supernatant is removed
Me3SiN3À B(C6F5)3 (1,1 isomer)
by syringe and discarded. The remaining crystals are dried
(1·10À 3 mbar) at À 20 C (isopropanol bath) for 20 minutes. The
To a degassed suspension of tris(pentafluorophenyl)borane B(C6F5)
3 (212 mg, 0.41 mmol) in toluene (1.5 mL), azidotrimethylsilane
Me3SiN3 (58 mg, 0.50 mmol, ~67 μL) was added via μL-syringe. The
suspension became clear within a few seconds and after a few
more seconds a precipitate was observed. The precipitate was
dissolved by heating the solution to 100 C (oil bath). Colorless
single crystals suitable for X-ray structure elucidation were grown
°
crystals were rather unstable and decomposed within a few
minutes at ambient temperatures.
C4H9Cl3GaNOSi (291.29 g·molÀ 1): 1H NMR (25 C, toluene-d8,
°
13
°
500.13 MHz): δ=À 0.17 (s, 9H, (CH3)3Si, 1J(1HÀ C)=122 Hz, 2J-
29
13
1
(1HÀ Si)=7 Hz). C{ H} NMR (25 C, toluene-d8, 125.8 MHz): δ=
°
29
°
À 0.7 (s, (CH3)3Si, 1J(13CÀ Si)=60 Hz), 137.1 (s, NCO). 14N{1H} NMR
by cooling the solution overnight to 5 C. The supernatant is
°
(25 C, toluene-d8, 36.1 MHz): δ=À 335.4 (br, 1 N, NCO, Δν1/2
=
removed by syringe and discarded. The remaining crystals are dried
15
(1·10À 3 mbar) at 40 C for 30 minutes, yielding 182 mg (0.29 mmol,
°
°
430 Hz), À 325.6 (br, 1 N, NCO, Δν1/2 =510 Hz). N NMR (25 C,
29
°
toluene-d8, 50.7 MHz): δ=À 327.1 (s, NCO). Si INEPT NMR (25 C,
71%) of azidotrimethylsilane tris(pentafluorophenyl)borane adduct
2
29
toluene-d8, 99.4 MHz): δ=6.0 (dec, (CH3)3SiNCO, J(1HÀ Si)=7 Hz).
[Me3SiN3À B(C6F5)3 (1,1 isomer)].
Raman (532 nm, 13.5 mW, 10 s, 30 acc., 25 C, cmÀ 1): 2977 (1), 2911
°
C21H9BF15N3Si (627.19 g·molÀ 1): mp. 120 C, 189 C (dec.). EA calc.
°
°
(5), 2326 (1), 2253 (1), 2240 (1), 1537 (1), 1460 (0), 1398 (1), 1324 (1),
1317 (6), 1258 (1), 1215 (1), 996 (1), 803 (1), 772 (1), 712 (1), 636 (2),
609 (1), 431 (1), 394 (10), 365 (5), 280 (6).
1
(found), %: C, 40.22 (39.79); H, 1.45 (1.53); N, 6.70 (6.66). H NMR
(25 C, CD2Cl2, 300.13 MHz): δ=0.34 (s, 9H, CH3, 1J(1HÀ C)=
13
°
29
11
121.4 Hz, 2J(1HÀ Si)=6.9 Hz). B NMR (25 C, CD2Cl2, 96.29 MHz):
°
13
1
°
δ=20.7 (br, NB(C6F5)3, Δν1/2 =400 Hz). C{ H} NMR (25 C, CD2Cl2,
75.47 MHz): δ=À 1.4 (s, SiCH3, J(13CÀ Si)=60 Hz), 114.9 (br, ipso-
1
29
Me3SiSCNÀ B(C6F5)3 (1,3 isomer)
C6F5), 137.9 (dm, m-CF, 1J(13CÀ F)=252 Hz), 142.9 (dm, p-CF,
19
19
19
1J(13CÀ F)=256 Hz), 148.6 (dm, o-CF, 1J(13CÀ F)=246 Hz). 14N{1H}
Tris(pentafluorophenyl)borane B(C6F5)3 (256 mg, 0.50 mmol) was
dissolved in isothiocyanotrimethylsilane Me3SiNCS (1.02 mg,
7.75 mmol, ~1.2 mL). Colorless single crystals suitable for X-ray
structure elucidation were grown by storing the degassed solution
°
NMR (25 C, CD2Cl2, 36.14 MHz): δ=À 323.3 (br, SiÀ NNN, Δν1/2
=
2300 Hz), δ=À 172.1 (br, SiÀ NNN, Δν1/2 =950 Hz), δ=À 143.5 (br,
19
1
°
SiÀ NNN, Δν1/2 =35 Hz). F{ H} NMR (25 C, CD2Cl2, 282.40 MHz): δ=
13
À 162.7 (m, 6F, m-CF, 1J(19FÀ C)=252 Hz), À 151.4 (m, 3F, p-CF,
°
for 2 weeks at À 20 C (refrigerator). The supernatant is removed by
13
13
1J(19FÀ C)=256 Hz), À 131.3 (m, 6F, o-CF, 1J(19FÀ C)=246 Hz). 29Si
syringe and discarded. The remaining crystals are dried
(1·10À 3 mbar) at 25 C for 1 hour, yielding 72 mg (0.11 mmol, 22%)
INEPT NMR (25 C, CD2Cl2, 59.63 MHz): δ=32.8 (dec, SiCH3, 2J-
°
°
29
1
( SiÀ H)=6.9 Hz). Raman (633 nm, 8 mW, 15 s, 20 acc., 25 C, cmÀ 1):
2987 (1), 2967 (1), 2920 (2), 2535 (1), 2163 (1), 1651 (3), 1646 (3),
1520 (1), 1385 (2), 1375 (1), 1204 (1), 875 (1), 857 (1), 839 (1), 787
(1), 774 (1), 757 (1), 747 (1), 708 (1), 682 (1), 653 (1), 636 (5), 593 (1),
579 (10), 549 (1), 490 (5), 475 (4), 446 (6), 417 (4), 405 (2), 393 (4),
376 (1), 358 (2), 347 (1), 316 (1), 306 (1), 284 (1), 243 (2), 232 (1). MS
(CI+, m/z (%)): 73 (8) [(CH3)3Si]+, 116 (55) [(CH3)3SiN3H]+, 188 (100)
of thiocyanotrimethylsilane tris(pentafluorophenyl)borane adduct
[Me3SiSCNÀ B(C6F5)3 (1,3 isomer)]. The isolated crystals are rather
unstable at ambient temperature. In the elemental analysis, the
adduct is present in a 2:1 ratio with the borane. In NMR spectra the
adduct is very labile, so that Me3SiSCNÀ B(C6F5)3 (1,3 isomer) and
Me3SiNCÀ B(C6F5)3 can be observed, which is also indicated by a
yellow coloration of the reaction solution.
°
*
[(CH3)3SiÀ N3À Si(CH3)3]+, 512 (68) [B(C6F5)3]
.
+
C22H9BF15NSSi (643.26 g·molÀ 1): mp. 108 C. EA calc. (found), %: C,
°
1
41.41 (42.29); H, 1.01 (1.04); N, 1.56 (1.44); S, 3.57 (3.87). ). H NMR
11
°
°
(25 C, CD2Cl2, 300.13 MHz): δ=0.60 (br, 9H, CH3). B NMR (25 C,
CD2Cl2, 96.29 MHz): δ=À 10.7 (br, Me3SiSCNÀ B(C6F5)3, Δν1/2 =75 Hz)
Me3SiN3À GaCl3 (1,1 isomer)
Gallium trichloride GaCl3 (180 mg, 1.02 mmol) was dissolved in
toluene (1 mL) resulting in a slightly yellow solution. The solution
became colorless within a few seconds by adding azidotrimeth-
13
1
°
À 22.2 (br, Me3SiCNÀ B(C6F5)3, Δν1/2 =75 Hz). C{ H} NMR (25 C,
CD2Cl2, 75.47 MHz): δ=0.5 (s, NCSiCH3), 1.8 (s, NCSSiCH3), 114.5 (br,
19
ipso-C6F5), 137.7 (dm, m-CF, 1J(13CÀ F)=249 Hz), 141.1 (dm, p-CF,
19
19
°
1J(13CÀ F)=251 Hz), 145.1 (br, CN), 148.4 (dm, o-CF, 1J(13CÀ F)=
ylsilane Me3SiN3 (132 mg, 1.15 mmol) at À 40 C (isopropanol bath).
19
1
°
245 Hz). F{ H} NMR (25 C, CD2Cl2, 282.40 MHz): δ=À 162.5 (m, 6F,
Colorless single crystals suitable for X-ray structure elucidation were
grown by cooling the solution overnight from ambient temper-
13
m-CF (Me3SiNCS), 1J(19FÀ C)=249 Hz), À 162.1 (m, 6F, m-CF
13
°
(Me3SiNC), 1J(19FÀ C)=249 Hz), À 157.4 (m, 3F, p-CF (Me3SiNCS),
atures to À 20 C (refrigerator with isopropanol bath). The crystals
13
13
1J(19FÀ C)=251 Hz), À 157.2 (m, 3F, p-CF (Me3SiNC), 1J(19FÀ C)=
were identified as Me3SiN3À GaCl3 adduct (1,1 isomer). The super-
13
251 Hz), À 133.1 (m, 6F, o-CF (Me3SiNCS), 1J(19FÀ C)=245 Hz),
natant is removed by syringe and discarded. The remaining crystals
13
are dried (1·10À 3 mbar) at À 20 C for 20 minutes. The crystals were
°
À 132.7 (m, 6F, o-CF (Me3SiNC), 1J(19FÀ C)=245 Hz). 29Si INEPT NMR
1
(25 C, CD2Cl2, 59.63 MHz): δ=20.7 (dec, CNSiCH3, 2J(29SiÀ H)=
°
rather unstable and decomposed within a few minutes at ambient
temperatures.
2
1
7.4 Hz), 46.7 (dec, SCNSiCH3, J(29SiÀ H)=7.4 Hz). IR (ATR, 32 scans,
25 C, cmÀ 1)*: 569 (m), 577 (m), 592 (m), 619 (m), 633 (m), 665 (m),
°
C3H9SiN3GaCl3 (291.29 g·molÀ 1): 1H NMR (25 C, Toluol-d8,
300.13 MHz): δ=0.01 (s), 0.21 (s). Si INEPT NMR (25 C, Toluol-d8,
°
679 (m), 739 (m), 773 (m), 798 (m), 835 (m), 854 (m), 968 (s), 1097
(s), 1259 (m), 1284 (m), 1381 (m), 1456 (vs), 1518 (s), 1601 (m), 1645
(m), 2015 (w), 2056 (w), 2094 (m), 2154 (w), 2173 (w), 2187 (w), 2197
(w), 2212 (w), 2245 (w), 2966 (w), 3304 (w), 3552 (w), 3676 (w).
29
°
59.63 MHz): δ=38.7 (m, SiCH3). A full set of analytical data could be
found in the literature.[32]
Raman (633 nm, 8 mW, 15 s, 20 acc., 25 C, cmÀ 1): 2975 (1), 2913 (1),
°
2541 (1), 2245 (10), 2214 (1), 2197 (1), 2196 (1), 1649 (1), 1521 (1),
1385 (1), 1315 (1), 1274 (1), 1262 (1), 1115 (1), 951 (1), 832 (1), 774
(1), 763 (1), 741 (1), 711 (1), 681 (1), 666 (1), 624 (3), 591 (1), 578 (4),
511 (1), 491 (5), 473 (1), 447 (3), 411 (2), 391 (3), 373 (2), 355 (1), 351
(1), 321 (1), 294 (1), 285 (1), 276 (1), 261 (1), 247 (1), 234 (1), 211 (1).
MS (CI+, m/z (%)): 106 (7) [Me3SiÀ SÀ H]+, 132 (100) [Me3SiÀ SCNÀ H]+,
163 (10) [Me3SiÀ NCSÀ SiMe2]+,204 (52) [Me3SiÀ NCSÀ SiMe3]+, 262
(17) [(Me3Si)2À NCSÀ C(CH3)3]+, 550 (7) [(Me3Si)2SCNÀ BH(C6F5)2]+.
Me3SiNCOÀ GaCl3 (1,1 isomer)
Gallium trichloride GaCl3 (155 mg, 0.88 mmol) was dissolved in an
excess of isocyanatotrimethylsilane (0.2 mL). The Lewis acid dis-
solved within 10 minutes at ambient temperatures. Colorless single
crystals suitable for X-ray structure elucidation were grown by
cooling the degassed solution overnight from ambient temper-
°
atures to À 40 C (isopropanol bath). The crystals were identified as
Eur. J. Inorg. Chem. 2021, 1–9
www.eurjic.org
6
© 2021 The Authors. European Journal of Inorganic Chemistry published
by Wiley-VCH GmbH
��
These are not the final page numbers!

Full Papers
doi.org/10.1002/ejic.202100237
[4] K.-A. Østby, G. Gundersen, A. Haaland, H. Nöth, Dalton Trans. 2005,
*
measured under non-inert conditions, hydrolysis (signals
>3300 cmÀ 1
)
2284–91.
[5] C. Loschen, K. Voigt, J. Frunzke, A. Diefenbach, M. Diedenhofen, G.
Frenking, Z. Anorg. Allg. Chem. 2002, 628, 1294.
[6] M. F. Ibad, P. Langer, A. Schulz, A. Villinger, J. Am. Chem. Soc. 2011, 133,
21016–21027.
Me3SiNCSÀ GaCl3 (1,3 isomer)
[7] M. F. Ibad, A. Schulz, A. Villinger, Organometallics 2019, 38, 1445–1458.
[8] M. F. Ibad, A. Schulz, A. Villinger, Organometallics 2015, 34, 3893–3901.
[9] A. Haaland, Angew. Chem. Int. Ed. 2006, 101, 1017–1032.
[10] W. E. Piers, T. Chivers, Chem. Soc. Rev. 1997, 26, 345–354.
[11] E. I. Davydova, T. N. Sevastianova, A. V. Suvorov, A. Y. Timoshkin, Coord.
Chem. Rev. 2010, 254, 2031–2077.
[12] F. Focante, P. Mercandelli, A. Sironi, L. Resconi, Coord. Chem. Rev. 2006,
250, 170–188.
[13] D. W. Stephan, G. Erker, Angew. Chem. Int. Ed. 2010, 49, 46–76; Angew.
Chem. 2010, 122, 50–81.
Gallium trichloride GaCl3 (180 mg, 1.05 mmol) was dissolved in
°
CH2Cl2 (0.5 mL). The degassed solution was cooled to À 20 C
(isopropanol bath) and isothiocyanotrimethylsilane (135 mg,
1.03 mmol) was added via μL-syringe. Colorless single crystals
suitable for X-ray structure elucidation were grown by cooling the
°
°
degassed solution overnight from À 20 C to À 40 C (isopropanol
bath). The crystals were identified as isothiocyanotrimethylsilane
gallium trichloride adduct Me3SiNCSÀ GaCl3 (1,3 isomer). The super-
natant is removed by syringe and discarded. The remaining crystals
are dried (1·10À 3 mbar) À 20 C for 20 minutes. The crystals were
[14] M. Lehmann, A. Schulz, A. Villinger, Angew. Chem. Int. Ed. 2009, 48,
°
7444–7447; Angew. Chem. 2009, 121, 7580–7583.
rather unstable and decomposed within a few minutes at temper-
[15] K. Bläsing, J. Bresien, R. Labbow, D. Michalik, A. Schulz, M. Thomas, A.
Villinger, Angew. Chem. Int. Ed. 2019, 58, 6540–6544; Angew. Chem.
2019, 131, 6610–6615.
[16] K. Bläsing, J. Bresien, R. Labbow, A. Schulz, A. Villinger, Angew. Chem.
Int. Ed. 2018, 57, 9170–9175; Angew. Chem. 2018, 130, 9311–9316.
[17] C. Aubauer, E. Irran, C. Keck, T. M. Klapötke, W. Schnick, A. Schulz, J.
Senker, Phosphorus Sulfur Silicon Relat. Elem. 2001, 169, 189–192.
[18] C. Aubauer, E. Irran, T. M. Klapötke, W. Schnick, A. Schulz, J. Senker,
Inorg. Chem. 2001, 40, 4956–4965.
[19] C. Hubrich, D. Michalik, A. Schulz, A. Villinger, Z. Anorg. Allg. Chem. 2008,
634, 1403–1408.
[20] I. Krossing, I. Raabe, Angew. Chem. Int. Ed. 2004, 43, 2066–90; Angew.
Chem. 2004, 116, 2116–2142.
°
atures about 0 C.
C4H9Cl3GaNSSi (307.36 g·molÀ 1): 1H NMR (25 C, toluene-d8,
°
500.13 MHz): δ=À 0.15 (s, 9H, (CH3)3SiÀ NÀ Ga), À 0.09 (s, 9H,
13
1
°
(CH3)3SiÀ NCSÀ Ga). C{ H} NMR (25 C, toluene-d8, 125.8 MHz): δ=
À 1.5 (s, (CH3)3Si, 1J(13CÀ Si)=60 Hz), 132.3 (s, NCS). 14N{1H} NMR
29
°
(25 C, toluene -d8, 36.1 MHz): δ=À 223.1 (s, 1 N, NCS, Δν1/2
=
29
°
90 Hz), À 204.4 (br, 1 N, NCS, Δν1/2 =360 Hz). Si INEPT NMR (25 C,
toluene -d8, 99.4 MHz): δ=22.8 (dec, (CH3)3SiNCS, J(1HÀ Si)=7 Hz).
2
29
Raman (532 nm, 13.5 mW, 10 s, 20 acc., 25 C, cmÀ 1): 2969 (2), 2906
°
(8), 2782 (1), 2174 (8), 1421 (1), 1391 (1), 1275 (1), 1264 (1), 867 (1),
772 (1), 713 (0), 631 (7), 492 (1), 389 (2), 356 (10), 296 (2), 266 (2),
252 (2), 210 (2).
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Acknowledgements
The “Deutsche Forschungsgemeinschaft” (DFG SCHU 1170/12-1) is
acknowledged for financial support (K.B.). We also thank the
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Conflict of Interest
The authors declare no conflict of interest.
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Keywords: Adducts
Pseudohalogens · Rhodanides
·
Azides
·
Cyanates
·
Cyanides
·
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Manuscript received: March 22, 2021
Revised manuscript received: April 13, 2021
Accepted manuscript online: April 21, 2021
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www.eurjic.org
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© 2021 The Authors. European Journal of Inorganic Chemistry published
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These are not the final page numbers!

FULL PAPERS
Dr. K. Bläsing, Dr. J. Bresien, S.
Maurer, Prof. Dr. A. Schulz*, Dr. A.
Villinger
1 – 9
Trimethylsilyl Pseudohalide
Adducts of GaCl3 and B(C6F5)3
1,1- or 1,3-product, that is the
cal calculations show that the thermo-
dynamically favored product of the
gas phase is not always observed,
because many isomers with almost
the same energy can often be formed
so that solid state effects become
important.
question: When Me3SiÀ Psh
(Psh=pseudohalogen=CN, N3, OCN,
and SCN) is treated with Lewis acids
(LA) GaCl3 and B(C6F5)3, adducts such
as Me3SiÀ Psh·GaCl3 and Me3SiÀ Psh·B-
(C6F5)3 are formed. Quantum mechani-