Effect of temperature on B(C6F5)3-catalysed reduction of germanium alkoxides by hydrosilanes - a new route to germanium nanoparticles

Article abstract of DOI:10.1039/d0dt01555e

Reduction of Ge(OBu)₄with PhMe₂SiH catalyzed by B(C₆F₅)₃at ambient temperature leads to GeH₄. We discovered that a higher temperature (above 100 °C) completely changes the reaction course by producing germanium nanoparticles (Ge NPs) in high yield. This process provides a simple one-pot method for Ge NPs synthesis from readily available substrates under mild conditions.

Full text of DOI:10.1039/d0dt01555e

View Article Online
View Journal
Dalton
Transactions
An international journal of inorganic chemistry
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: S. Rubinsztajn, U.
Mizerska, J. Zakrzewska, P. Uznanski, M. Cypryk and W. Fortuniak, Dalton Trans., 2020, DOI:
10.1039/D0DT01555E.
Volume 46
Number 10
14 March 2017
Pages 3073-3412
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Dalton
Transactions
An international journal of inorganic chemistry
Accepted Manuscripts are published online shortly after acceptance,
before technical editing, formatting and proof reading. Using this free
rsc.li/dalton
service, authors can make their results available to the community, in
citable form, before we publish the edited article. We will replace this
Accepted Manuscript with the edited and formatted Advance Article as
soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes to the
text and/or graphics, which may alter content. The journal’s standard
Terms & Conditions and the Ethical guidelines still apply. In no event
ISSN 0306-0012
COMMUNICATION
Douglas W. Stephen et al.
shall the Royal Society of Chemistry be held responsible for any errors
N-Heterocyclic carbene stabilized parent sulfenyl, selenenyl,
and tellurenyl cations (XH+, X = S, Se, Te)
or omissions in this Accepted Manuscript or any consequences arising
from the use of any information it contains.
rsc.li/dalton

Please do not adjust margins
Page 1 of 6
Dalton Transactions
View Article Online
DOI: 10.1039/D0DT01555E
COMMUNICATION
Effect of Temperature on B(C6F5)3-Catalysed Reduction of
Germanium Alkoxides by Hydrosilanes – A New Route to
Germanium Nanoparticles
Received 00th January 20xx,
Accepted 00th January 20xx
Slawomir Rubinsztajna*, Urszula Mizerskaa, Joanna Zakrzewskaa, Pawel Uznanskia, Marek Cypryka,
and Witold Fortuniaka
DOI: 10.1039/x0xx00000x
Reduction of Ge(OBu)4 with PhMe2SiH catalyzed by B(C6F5)3 at silyl hydrides, we decided to evaluate the effect of temperature
ambient temperature leads to GeH4. We discovered that a higher on the yield of GeH4 generated.
temperature (above 100 °C) completely changes the reaction
We report here that the reaction of the same reagents
course by producing germanium nanoparticles (Ge NPs) in high carried out at elevated temperature, above 100 °C,
yield. This process provides a simple one-pot method for Ge NPs unexpectedly proceeds in a different direction. The anticipated
synthesis from readily available substrates under mild conditions.
process of functional group exchange is dominated by reduction
of Ge(OBu)4 to Ge0 and formation of Ge NPs.
In the typical experiment, a premade solution of 2.46 × 10-3
mol of PhMe2SiH with 1.26 × 10-5 mol of B(C6F5)3 (0.5 mol% vs
SiH) in 12 mL of toluene was added dropwise over a period of
10 minutes to the solution of 5.5 ×10-4 mol of Ge(OBu)4 in 2.5
mL of toluene at desired temperature. The reaction studied was
carried out at five temperatures 20 °C, 40 °C, 60 °C, 80 °C and
One of the important reactions of silyl hydrides is their
dehydrocarbonative condensation with alkoxysilanes promoted
by tris(pentafluorophenyl)borane (TPFPB), which leads to the
formation of a siloxane bond (Si-O-Si) and release of a benign
hydrocarbon as a by-product. This process, also known as the
Piers-Rubinsztajn reaction,1-3 opens a new path to efficient and
selective synthesis of a wide range of siloxane materials,
including various siloxane copolymers,4-8 highly branched
siloxane resins9, 10 and well-defined siloxane oligomers.11-13 This
reaction was successfully applied to preparation of crosslinked
silicones14 and modification of silica,15 carbon nanotubes16 and
graphene oxide surfaces.17 A few years ago, we became
interested in extending this chemistry to the formation of other
heterosiloxane bonds such as B-O-Si and Ge-O-Si. Indeed, the
reaction of trimethyl borate with silyl hydrides in the presence
1
100 °C (Figure 1). The progress of reaction was followed by H
NMR (ESI Figures S1 and S2) IR and UV spectroscopy.
Additionally, the final samples were analysed by 29Si NMR (ESI
Figure S3). The final 1H NMR spectra of the reaction carried out
at 20 °C (ESI Figure S1) and at 100 °C (ESI Figure S2) show the
complete conversion of PhMe2SiH and Ge(OBu)4 and almost
quantitative formation of PhMe2SiOBu (ESI Figure S3), which is
consistent with the functional group exchange process reported
earlier.20 However, the appearance of the final reaction
mixtures obtained at the temperature above 80 °C is very
different from the appearance of the colourless final reaction
mixture carried out at 20 °C, Figure 1.
of catalytic amounts of TPFPB produces borosiloxane resin with
19
high yield.18,
However, our attempt to create a
germanosiloxane bond in an analogous process failed. The
room temperature reaction of germanium tetrabutoxide
(Ge(OBu)4) with dimethylphenylsilane (PhMe2SiH) catalysed by
TPFPB in toluene proceeded smoothly to the complete
consumption of reactants and almost quantitative formation of
GeH4 and PhMe2SiOBu.20 To better understand this surprisingly
selective exchange of functional groups between Ge(OBu)4 and
a. Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences,
Sienkiewicza 112, Lodz, 90-363, Poland
*E-mail: srubin@cbmm.lodz.pl
Figure 1. The effect of temperature on the appearance of the final reaction
mixture of 1 molar eq. of Ge(OBu)4 with 5 molar eq. of PhMe2SiH in toluene in the
presence of B(C6F5)3.
†Electronic Supplementary Information (ESI) available: [Experimental procedures,
NMR spectra, selected UV-Vis spectra, TEM, SEM images, XPS and EDS results, DLS
analysis, and description of DFT calculation]. See DOI: 10.1039/x0xx00000x
Please do not adjust margins

Please do not adjust margins
Dalton Transactions
Page 2 of 6
COMMUNICATION
Journal Name
Surprisingly, the final reaction mixture completed above 80 °C
has an intense dark red colour. The colour of the reaction
mixture performed at 100 °C gradually changed to yellow over
View Article Online
DOI: 10.1039/D0DT01555E
1
a period of 2 h (Figure 2). H NMR spectrum of the sample
withdrawn after 2 h of reaction showed about 50% conversion
of Ge(OBu)4 (ESI Figure S4). Under these conditions, no further
substrates consumption or colour change was observed. An
additional portion of catalyst (0.5 mol% relative to SiH) was
needed to achieve complete Ge(OBu)4 conversion and to create
corresponding amount of PhMe2SiOBu (ESI Figures S2 and S3).
Furthermore, gas formation was observed during the silane
addition and after the second portion of catalyst was
introduced. A further change in the colour of the reaction
mixture from yellow to dark red was observed after an
additional 120 minutes of heating at 100 °C (Figure 2). The
observed stopping of the reaction can be explained by the loss
of B(C6F5)3 catalytic activity under these conditions.
Decomposition of B(C6F5)3 in the presence of Si-H and Ge-H
compounds at elevated temperature has been observed before.
It can be explained by the migration of the C6F5 group from
borane to Si or Ge (Equation 1).21, 22
Figure 3. (A) HAADF TEM images of the Ge NPs aggregates prepared in reaction of
1 molar eq. of Ge(OBu)4 with 5 molar eq. of PhMe2SiH in the presence of 2 × 0.5
mol% B(C6F5)3 in toluene at 100 °C; (B) EDS spectrum of the same area.
The EDS spectrum of the tested sample (Figure 3B) confirmed
the high content of germanium. Oxygen, silicon, and carbon
were also detected. The presence of these elements can be
explained by the formation of high-boiling organosilane and
disiloxane in this process (PhMe2SiOBu and PhMe2SiOSiMe2Ph)
and the possible partial oxidation of Ge0 to GeOx during sample
preparation. The Ge NPs formed were subsequently isolated by
removing toluene and other volatile compounds by stripping
under high vacuum at 100 °C, followed by washing the
remaining solid with dry heptane. This procedure produced a
dark orange powder. Scanning electron microscopy (SEM) in
combination with energy-dispersive spectroscopic analysis
(EDS) indicates that the resulting powder consists of 79% by
weight of Ge. Oxygen, residual carbon, silicone, and fluorine
have also been found similarly to TEM/EDS analysis (ESI Figure
S8). The presence of Ge0 as well as various germanium oxides
on the powder surface was confirmed by X-ray photoelectron
spectroscopy (XPS). The curve fitting of the 3d spectrum reveal
presence of Ge0, and complex mixture of germanium oxides
GeOx (2>x>0) with binding energy 30.5 eV and 32.5 eV
respectively, (ESI Figure S9).29-31
B(C6F5)3 + R3SiH → HB(C6F5)2 + R3SiC6F5
(Equation 1)
Red colour formation was also monitored by UV-Vis
spectroscopy (ESI Figure S5). The collected spectra show a
gradual increase in the broad absorption band, which over time
extends into a visible light region. The intersection of the
tangent to the UV curve and the X abscissa, shifts from 340 nm
(ESI Figure S5, curve 15 min) to 580 nm (ESI Figure S5, curve 214
min). The observed colour change from colourless to yellow,
and finally dark red can be attributed to the formation of Ge NPs
and a gradual increase in their size. This conclusion is consistent
with previously published UV-Vis absorption spectra of Ge NPs
synthesized in solution.23-27 The particles formed are difficult to
observe by conventional transmission electron microscopy
(TEM) due to their amorphous nature, which was confirmed by
the diffuse ring pattern of fast Fourier transformations (FFTs) of
the TEM image (ESI Figure S6).28 The presence of clusters of
amorphous Ge NPs in size below 5 nm has been verified on TEM
images collected using the high-angle annular dark-field
mode (HAADF), which is very sensitive to the differences in the
atomic number (Z-contrast) of the elements present (Figure 3A)
as well as DLS analysis (ESI Figure S7).
To obtain more information about the process under study,
the Ge concentration retained in the final reaction mixtures was
measured by X-ray fluorescence spectroscopy (XRF), Table 1.
Table 1. The effect of temperature on % by weight of Ge present in the final solutions
after reaction 1 molar eq. of Ge(OBu)4 with 5 molar eq. PhMe2SiH in the presence of
B(C6F5)3.
Reaction Temp. /
Solvent
[Ge] / wt%
% Yield of Ge
°C
20
Toluene
Toluene
0.037
0.044
0.04
14
16
15
46
85
80
95
40
60
Toluene
80
Toluene
0.115
0.218
0.212
0.253
100
130
160
Toluene
Figure 2. Observed colour changes as a function of time during reaction of 5 molar
eq. of PhMe2SiH and 1 molar eq. of Ge(OBu)4 in the presence of B(C6F5)3 in toluene
at 100 °C.
Mesitylene
Mesitylene
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 6
Dalton Transactions
Please do not adjust margins
Journal Name
COMMUNICATION
Table 2. DFT calculations of the standard Gibbs free energies, ΔG298 [Kcal/mol] of
It should be noted that the solvent used was changed from
toluene to higher boiling mesitylene in order to carry out the
reaction at 130 °C and 160 °C. The yield of Ge NPs suspended in
toluene or mesitylene solutions exceeding 80% was achieved at
temperatures above 100 °C.
View Article Online
possible model reactions in the system: Ge(OMe)4 + Me3SiH at 298 K in the gas phase
DOI: 10.1039/D0DT01555E
conditions.
Eq.
#
Reaction
ΔG298
Freshly obtained Ge NPs red dispersions did not show any
photoluminescence in the visible light region after irradiation
with 350 nm or 475 nm light. The red colour is stable for samples
stored under dry nitrogen for many months. However, the red
colour slowly fades and produces a colourless transparent
dispersion when exposed to dry oxygen or ambient air over a
period of many days. This phenomenon could be explained by
the partial oxidation of Ge NPs, which are sensitive to the
presence of oxygen due to their amorphous nature. The
collected emission spectra for the colourless dispersions exhibit
blue luminescence with maximum around 468 nm when excited
with 375 nm light, Figure 4. Only the blue emission was
observed regardless of the size of the nanoparticles, which
suggests that the classic quantum confinement effect is not
responsible for photoluminescence in the system under
study.32, 33 Fluorescence spectra are sensitive to the excitation
wavelength. The observed maximum of fluorescence emission
shifts to red when the excitation wavelength also shifts into the
longer wavelength, Figure 4. This phenomenon implies that
there are multiple populations of surface traps of different
energy responsible for photoluminescence. The chemical
nature of photo-active species has not been determined. It may
be associated with the various defects in the amorphous Ge NPs
core or nonhomogeneous GeOx coating on the Ge nanoparticles
surface.34-37
2
Ge(OMe)4 + 4Me3SiH → 4 Me3SiOMe + GeH4
Ge(OMe)4 + 4Me3SiH → 4 Me3SiOMe + 2H2 + Ge0
Ge(OMe)4 + 4Me3SiH → 4 Me3SiOMe + 2H2 + Ge0
Ge(OMe)4 + Me3SiH → Me3SiOMe + (MeO)3GeH
-64.8
-8.6
3
(g)
(s)
4
-87.7
-15.7
-15.2
-14.8
-19.1
3.1
5
6
(MeO)3GeH + Me3SiH → Me3SiOMe + (MeO)2GeH2
(MeO)2GeH2 + Me3SiH → Me3SiOMe + (MeO)GeH3
(MeO)GeH3 + Me3SiH → Me3SiOMe + GeH4
(MeO)3GeH → (MeO)2Ge(II) + MeOH
7
8
9
10
11
12
(MeO)2GeH2 → (MeO)2Ge(II) + H2
-3.5
2(MeO)2Ge(II) → (MeO)4Ge + Ge0
59.7
-19.4
(g)
2(MeO)2Ge(II) → (MeO)4Ge + Ge0
(s)
The correctness of the proposed Equation 3 was confirmed by
the almost stoichiometric formation of PhMe2SiOBu (ESI Figures
S2 and S3), high germanium retention efficiency in the reaction
mixture (Table 1) and the release of about 2 molar equivalents
of gas per 1 molar equivalent of Ge(OBu)4 (ESI Figure S10).
Mechanism of the discovered reaction is not well
understood. Our previous research shows that the formation of
GeH4 (Equation 2, Table 2), occurs at room temperature
through a chain of four consecutive reactions (Equations 5 - 8,
Table 2).20 The final product, GeH4, is highly volatile gas (Bp = -
88 °C) and quickly evaporates from the reaction mixture. It is
very unlikely that Ge0 arises from the direct GeH4
decomposition as recently proposed for the production of
germanium nanowires in supercritical toluene at 500 °C.38 The
reaction chain (Equations 5 - 8, Table 2) had to be interrupted
by a competitive process when the reaction temperature rose
above 100 °C. It is possible that reductive elimination of alcohol
(Equation 9, Table 2) or hydrogen (Equation 10, Table 2)
compete with the formation of GeH4 according to Scheme 1.
It is remarkable that the reaction of Ge(OBu)4 with
PhMe2SiH in the presence of B(C6F5)3 carried out at 20 °C gives
GeH4 gas in almost quantitative yield according to Equation 2,
Table 2, but the reaction mixture of the same reagents heated
to 100 °C produces Ge0 with high efficiency according to
Equation 3, Table 2.
Scheme 1. The proposed mechanism of Ge0 formation.
These two reactions are unimolecular, so their activation
entropy component can cause their dominance over the
bimolecular process of functional group exchange as the
reaction temperature increases. The metastable Ge(II)(OBu)2
generated this way may then disproportionate to Ge0 and
Ge(OBu)4 (Equation 11, Table 2). The so-formed atomic Ge0
aggregates by self-nucleation into clusters and eventually
creates amorphous Ge NPs. Ge(OBu)4 is recycled to the
Figure 4. Normalized photoluminescence spectra of the dispersions of Ge NPs
obtained during reaction of 5 molar eq. of PhMe2SiH and 1 molar eq. of Ge(OBu)4
in the presence of B(C6F5)3 in toluene at 100 °C and subsequently exposed to
ambient air for many days.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please do not adjust margins
Dalton Transactions
Page 4 of 6
COMMUNICATION
Journal Name
M. Gretton, B. Kamino, M. Brook and T. Bender,
S. Tian, J. Li, Z. Cai, B. Shi, W. Chen andDYO. IC: h10e.n10g3,9E/uDr0.DPTo0l1y5m55.E
J., 2018, 108, 373-379.
L. Ai, Y. Chen, L. He, Y. Luo, S. Li and C. Xu, Chem. Comm.,
2019, 55, 14019-14022.
J. Chojnowski, S. Rubinsztajn, W. Fortuniak and J. Kurjata,
Macromolecules, 2008, 41, 7352-7358.
6
7
8
9
functional group exchange process until complete consumption
of PhMe2SiH.
View Article Online
Macromolecules, 2012, 45, 723-728.
The disproportionation of Ge(II) precursors to Ge0 and Ge(IV)
is well known in the literature but usually requires a
temperature much higher than 100 °C. GeI2 disproportionation
at a temperature above 210 °C was previously used for the
deposition of crystalline Ge and for the synthesis of Ge NPs.27,
10 J. Kurjata, W. Fortuniak, S. Rubinsztajn and J. Chojnowski,
Eur. Polym. J., 2009, 45, 3372-3379.
11 D. Thompson and M. Brook, J. Am. Chem. Soc., 2008, 130,
32-33.
12 J. Li, Z. Zhang, T. Zhu, Z. Li, J. Wang and Y. Cheng, Eur. Polym.
J., 2020, 109562.
13 K. Matsumoto, S. Shimada and K. Sato, Chem. Eur. J., 2019,
25, 920-928.
39-41
Recently, the disproportionation of diphenylgermylene,
Ph2Ge, at 300 °C was proposed as the last step in the synthesis
of Ge NPs from Ph3GeX, where X = Cl, Br.28 The synthesis of
germanium nanowires by thermal decomposition of
germanium 2,6-dibutylphenoxide at 300 °C has also been
demonstrated.42
It should be mentioned that the standard Gibbs free energy
for the disproportionation of Ge(OBu)2 calculated for the gas
phase conditions is thermodynamically unfavourable. The
Ge(II)(OBu)2 disproportionation becomes thermodynamically
allowed when the standard Gibbs free energy of Ge0 transition
from the gas phase (Ge0(g)) to the solid phase (Ge0(s)), estimated
at -79.1 kcal/mol, 43 is taken into account (Equation 12, Table 2).
14 J. Grande, A. Fawcett, A. McLaughlin, F. Gonzaga, T. Bender
and M. Brook, Polymer, 2012, 53, 3135-3142.
15 J. Escorihuela, S. Pujari and H. Zuilhof, Langmuir, 2017, 33,
2185-2193.
16 R. Chadwick, J. Grande, M. Brook and A. Adronov,
Macromolecules, 2014, 47, 6527-6530.
17 J. Zhang, S. Liang, L. Yu, A. Skov, H. Etmimi, P. Mallon, A.
Adronov and M. Brook, J. Polym. Sci. Pol. Chem., 2016, 54,
2379-2385.
18 S. Rubinsztajn, J. Inorg. Organomet. Polym. Mater., 2014, 24,
1092-1095.
19 F. Drozdov, S. Milenin, V. Gorodov, N. Demchenko, M. Buzin
and A. Muzafarov, J. Organomet. Chem., 2019, 891, 72-77.
20 S. Rubinsztajn, M. Cypryk, J. Chojnowski, W. Fortuniak, U.
Mizerska and P. Pospiech, Organometallics, 2018, 37, 1585-
1590.
21 D. J. Parks, W. E. Piers and G. P. A. Yap, Organometallics,
1998, 17, 5492-5503.
22 S. Rubinsztajn, J. Chojnowski, M. Cypryk, U. Mizerska, W.
Fortuniak and I. I. Bak-Sypien, J. Catal., 2019, 379, 90-99.
23 D. A. Ruddy, J. C. Johnson, E. R. Smith and N. R. Neale, ACS
Nano, 2010, 4, 7459-7466.
24 N. H. Chou, K. D. Oyler, N. E. Motl and R. E. Schaak, Chem.
Mater., 2009, 21, 4105-4107.
25 E. Muthuswamy, A. Iskandar, M. Amador and S. Kauzlarich,
Chem. Mater., 2013, 25, 1416-1422.
26 M. Rodio, A. Scarpellini, A. Diaspro and R. Intartaglia, J.
Mater. Chem. C, 2017, 5, 12264-12271.
Conclusions
In summary, we found a new process involving Si-H bond
activation by electron deficient boranes such as B(C6F5)3. The
discovered reaction of Ge(OBu)4 with Si-H functional silanes in
the presence of B(C6F5)3 carried out at temperatures above 100
°C produces Ge0 in high yield, which spontaneously aggregates
to amorphous Ge NPs. This process provides a simple one-pot
method for Ge NPs synthesis from readily available substrates
under mild conditions. We continue to study this new process
to answer intriguing mechanistic questions about the formation
of Ge NPs, the nature of photoluminescence observed, and
ways to optimize the Ge NPs synthesis. The results obtained will
be published in the full paper under development.
27 D. Vaughn, J. Bondi and R. Schaak, Chem. Mater., 2010, 22,
6103-6108.
Conflicts of interest
28 B. Pescara, K. A. Mazzio, K. Lips and S. Raoux, Inorg. Chem.,
2019, 58, 4802-4811.
There are no conflicts to declare.
29 D. Wang, Y.-L. Chang, Q. Wang, J. Cao, D. B. Farmer, R. G.
Gordon and H. Dai, J. Am. Chem. Soc., 2004, 126, 11602-
11611.
Acknowledgments
30 J. Hu, Q. Lu, C. Wu, M. Liu, H. Li, Y. Zhang and S. Yao,
Langmuir, 2018, 34, 8932-8938.
31 F. Li, J. Wang, S. Sun, H. Wang, Z. Tang and G. Nie, Small,
2015, 11, 1954-1961.
32 N. Shirahata, D. Hirakawa, Y. Masuda and Y. Sakka,
Langmuir, 2013, 29, 7401-7410.
The authors are grateful to Wacker Chemie AG for financial
support and permission to publish their results. DFT
calculations were supported by the PL-Grid infrastructure. We
thank Dr. Torsten Gottschalk-Gaudig for valuable discussions.
33 D. Carolan, Prog. Mater. Sci., 2017, 90, 128-158.
34 M. Zacharias and P. Fauchet, Appl. Phys. Lett., 1997, 71, 380-
382.
35 M. Zacharias and P. Fauchet, J. Non-Cryst. Solids, 1998, 227,
1058-1062.
36 H. Wu, M. Ge, C. Yao, Y. Wang, Y. Zeng, L. Wang, G. Zhang
and J. Jiang, Nanotechnology, 2006, 17, 5339.
37 A. Guleria, S. Neogy, D. K. Maurya and S. Adhikari, J. Phys.
Chem. C, 2017, 121, 24302-24316.
38 X. Lu, J. T. Harris, J. n. E. Villarreal, A. M. Chockla and B. A.
Korgel, Chem. Mater., 2013, 25, 2172-2177.
Notes and references
1
M. Brook, J. Grande, F. Ganachaud and A. Muzafarov, Silicon
Polymers, 2011, 235, 161-183.
2
3
M. Brook, Chem. Eur. J., 2018, 24, 8458-8469.
R. Wakabayashi and K. Kuroda, ChemPlusChem, 2013, 78,
764-774.
4
5
S. Rubinsztajn and J. Cella, Macromolecules, 2005, 38, 1061-
1063.
J. Cella and S. Rubinsztajn, Macromolecules, 2008, 41, 6965-
6971.
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 6
Dalton Transactions
Please do not adjust margins
Journal Name
COMMUNICATION
39 P. Reiss, M. Carriere, C. Lincheneau, L. Vaure and S. Tamang,
Chem Rev, 2016, 116, 10731-10819.
View Article Online
DOI: 10.1039/D0DT01555E
40 X. Lu, B. A. Korgel and K. P. Johnston, Chem. Mater., 2005,
17, 6479-6485.
41 D. T. Restrepo, K. E. Lynch, K. Giesler, S. M. Kuebler and R. G.
Blair, Mater. Res. Bull., 2012, 47, 3484-3488.
42 H. Gerung, T. J. Boyle, L. J. Tribby, S. D. Bunge, C. J. Brinker
and S. M. Han, J. Am. Chem. Soc., 2006, 128, 5244-5250.
43 W. Haynes, CRC Handbook of Chemistry and Physics. Boca
Raton: CRC Press, Taylor and Francis Group, 2013, 5.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Please do not adjust margins

Dalton Transactions
Page 6 of 6
View Article Online
DOI: 10.1039/D0DT01555E
The reaction of Ge(OBu)4 with PhMe2SiH in
the presence of B(C6F5)3 carried out at
temperatures above 100 °C provides a simple
one-pot method for Ge NPs synthesis under
mild conditions.