From Remote Alkenes to Linear Silanes or Allylsilanes depending on the Metal Center

Article abstract of DOI:10.1002/cctc.201800159

The selective synthesis of linear silanes or allylsilanes from remote alkenes was explored. The cationic, unsaturated, 16-electron hydrido–silyl–Rh^III complex was found to be an efficient catalyst for a tandem catalytic alkene isomerization–hyd

Full text of DOI:10.1002/cctc.201800159

Accepted Article
Title: From Remote Alkenes to Linear Silanes or Allyl Silanes
Depending on the Metal Centre
Authors: Susan Azpeitia, Antonio Rodriguez-Dieguez, María A.
Garralda, and Miguel A. Huertos
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COMMUNICATION
From Remote Alkenes to Linear Silanes or Allyl Silanes
Depending on the Metal Centre
[
a]
[b]
[a]
,[a],[c]
Susan Azpeitia, Antonio Rodriguez-Dieguez, María A. Garralda and Miguel A. Huertos*
Abstract: The selective synthesis of linear silanes or
allylsilanes from remote alkenes is reported. The cationic
and unsaturated, 16 electrons, hydrido-silyl-Rh(III)
complex is efficient catalysts for a tandem catalytic alkene
isomerization-hydrosilylation reaction at room temperature
under solvent-free conditions. The analogue hydrido-silyl-
Ir(III) complex is selective for the dehydrogenative
silylation, leading to the formation of terminal allylsilanes.
isomerization-hydrosilylation of internal alkenes catalysed by
[
14]
[15]
[6e,16]
iron,
nanoparticles
recently reported on a rhodium silyl complex containing a Si,S-
nickel
or cobalt
complexes or nickel
[
17]
have recently been reported. We have more
F
chelating ligand, {Rh(H)[SiMe
2
(o-C
6
H
4
SMe)](PPh
3
)
2
}[BAr
4
], as
[
18]
being a very efficient catalyst for this reaction.
These results
prompted us to evaluate the viability of related hydrido-silyl
rhodium(III) and iridium(III) complexes containing Si,S,S-
terdentate ligands as catalysts for the tandem isomerization-
hydrosilylation of terminal and internal alkenes.
Organosilane compounds are extensively employed in
Here, we report on the catalytic activity of the coordinatively
[
1]
commercial products, such as coatings, paints or sealants. They
also play a significant role in organic synthesis as useful
unsaturated
Rh(III)
compound
[RhH(SiMe(o-
F
[19]
C
6
H
4
SMe) )(PPh )][BAr ]
2
3 4
(compound 1 in Figure 1) in tandem
[
2]
intermediates in various synthetic transformations. Transition
metal-catalyzed hydrosilylation of alkenes is stablished as one of
isomerization-hydrosilylation of internal alkenes to form linear
silanes. Moreover, we describe the synthesis and
characterization of the coordinatively saturated Ir(III) compounds
[
3]
the most common preparation pathways for these compounds.
[
4]
[5]
Platinum catalysts based on Speier’s
and Karstedt’s
(
compounds
2-4
in
Figure
1). [IrH(SiMe(o-
complexes have remained powerful methods in hydrosilylation for
years, and first-row transition metals have also been recently
C6H4SMe)2)(PPh3)(THF)][BArF4] (compound 4 in Figure 1),
containing a labile solvent ligand (THF), is selective for the
dehydrogenative silylation of internal alkenes, leading to the
formation of terminal allyl silanes..
[
6]
studied. Unsaturated hydrosilylation products are also versatile
synthetic intermediates, based on their high stability and non-toxic
[
7]
nature. They can undergo direct transformations to allyl and
vinyl alcohols, or act as nucleophiles in reactions such as Hiyama
BArF
4
[
8]
Si
Ir
Si
or
Sakurai
coupling
reactions.
Although
catalysed
S
Ph3P
H
S
hydrosilylation of alkynes is the general route to these compounds,
dehydrogenative silylation of alkenes has likewise become a
Ph3P
H
Rh
S
S
Cl
[
9]
1
2
useful method of synthesis. For dehydrogenative silylation,
BArF
[
10]
4
precious metals like ruthenium or rhodium,
or more recent
Si
Ir
Si
[
11]
[12]
examples of iron
and cobalt
have proved to be efficient
S
S
H
H
Ph3P
H
Ir
catalysts. Studies of iridium complexes as catalysts in both
hydrosilylation and dehydrogenative silylation of alkenes are
S
S
O
PPh3
[
13]
rare. One common challenge for the mentioned systems is the
formation of terminal silylated products from internal olefins or
olefin mixtures. Internal olefin mixtures being more readily
accessible and cheaper than terminal alkenes also add to the
interest of this process. Examples of efficient tandem
3
4
Figure 1. Compounds used as precatalysts in this work.
The reaction of [Ir(cod)Cl]
tridentate proligand SiMeH(o-C
air-stable Ir(III) neutral
SMe) )(PPh )} (2) (Scheme 1). This compound was
2
with the equimolar amount of the
SMe) and PPh afforded the
complex {IrClH(SiMe(o-
6
H
4
2
3
[
a]
S. Azpeitia, U. Prieto, E. San Sebastián, M. A. Garralda, M. A.
Huertos
C
6
H
4
2
3
Departamento de Química Aplicada
Universidad del País Vasco (UPV/EHU)
Apartado 1072, 20080, San Sebastián, Spain
E-mail: miguelangel.huertos@ehu.es
A. Rodriguez-Dieguez
Departamento de Química inorgánica
Universidad de Granada
Avenida Fuentenueva s/n, 18071 Granada, Spain
M. A. Huertos
characterized in solution by NMR spectroscopy and ESI-MS.
Complex 2 is the iridium analogue to the precursor of the rhodium
complex 1.
[
b]
c]
[
IKERBASQUE, Basque Fundation for Science
48013, Bilbao, Spain
Scheme 1. Synthesis of Complex 2.
Supportinginformation and the ORCID identification number(s) for the
author(s) of this article can be found under:
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COMMUNICATION
1
The H NMR spectrum shows a doublet at -14.13 ppm (JP-H = 17.6
745.12), which corresponds to the ion {Ir[SiMe(o-
+
Hz) assigned to the hydrido resulting from the Si–H activation by
the metal centre. The signal corresponding to the SiMe unit
appears at δ 0.07, and the other two non-equivalent SMe signals
C
6
H
4
SMe)
2
](H)(PPh
3
)} due to loss of THF.
As mentioned previously in the introduction of this paper, we
thought useful to extend our studies on the reaction of silanes with
internal alkenes using hydrido-silyl-Rh(III) (1) and Ir(III)
complexes (2-4) containing terdentate Si,S,S-ligands as
precatalysts. Initial hydrosilylation experiments were performed
3
1
1
are observed at δ 2.65, and 3.41. The P{ H} NMR shows a
unique signal at 13.3 ppm that indicates Ir(III)
a
triphenylphosphine complex. An X-ray diffraction study of
complex 2 confirms the proposed structure based on NMR
spectroscopic data in solution (Figure 2a). The Ir(III) centre is in a
with an equimolar amount of predried trans-2-octene and Et
using 1 mol% loading of catalyst, without added solvent and under
an atmosphere of N (Table 1) The precatalysts used for this initial
3
SiH
6 4 2
pseudo-octahedral geometry. The pincer SiMe(o-C H SMe)
ligand adopts a facial disposition and is coordinated to the metal
center by a silyl fragment, and the two thioether moieties. Hydride
and triphenylphosphine occupy the two coordination positions
trans to sulphur atoms, while chloride is located trans to the silyl
unit.
2
.
catalysis experiments were (Figure 1): the unsaturated cationic
silyl-hydrido-Rh(III) compound 1, the neutral silyl-hydrido-
chloride-Ir(III) complex 2, the neutral silyl-dihydrido-Ir(III) complex
3 and the cationic silyl-hydrido-Ir(III) compound 4, which has a
labile THF molecule coordinated to the metal centre.
Overnight reaction of complex 2 with LiAlH
temperature allowed the exchange of chloride by hydride to yield
complex {Ir(H) [SiMe(o-C SMe) ](PPh )} (3) (Scheme 2).
Otherwise, addition of the NaBAr salt to complex 2 in CH Cl
4 2
in Et O at room
2
6
H
4
2
3
F
4
2
2
leads to removal of chloride, and subsequent dissolution in
tetrahydrofuran (THF) allows the formation of the cationic
F
compound {Ir[SiMe(o-C
6
H
4
SMe)
2
](H)(PPh
3
)(THF)}[BAr
4
]
(4)
(
Scheme 2), where the solvent would then occupy the
coordinative vacancy left by the chloride. Attempts to obtain the
Ir(III) analogue of 1 proved unsuccessful.
Figure 2 a) Molecular structure of 2. Displacement ellipsoids are drawn at 50%
probability level. b) Molecular structure of 3. Displacement ellipsoids are drawn
[
20]
at 50% probability level.
Scheme 2. Synthesis of Complexes 3 and 4.
1
The rhodium(III) complex 1 was able to catalyse the tandem
isomerization-hydrosilylation of trans-2-octene at room
temperature with a selectivity of 99% for the linear product
Experimental H NMR data for 3 shows a single signal for the
hydrido at -15.44 ppm (d, JP-H = 14.2 Hz), indicating the
equivalence of the two hydride ligands in the molecule. The
signals for the SiMe and the equivalent SMe units appear at 1.09
triethyloctylsilane
5 (Scheme 3a; Table 1, entry 1). 76%
3
1
1
conversion was reached after 12h reaction and further reaction
up to 72h allowed 90% conversion. Analogue iridium(III) complex
and 2.15 ppm respectively. The P{ H} NMR spectrum shows a
unique signal at 13.6 ppm corresponding to Ir(III)
a
4
also reached good conversion after 12h, though it require
triphenylphosphine complex. Isolation of X-ray quality crystals
allowed the characterization of compound 3 by single-crystal X-
ray structural determination (Figure 2b). The coordination
geometry for the Ir(III) centre is pseudo octahedral, with the
heating up to 50 ºC (Table 1, entry 4). However, the observed
main silylated compound for this catalyst was the unsaturated
allylic triethyl(2-octen-1-yl)silane 6, with a 60% selectivity; this fact
indicates that the main catalytic reaction occurring is a tandem
isomerization-dehydrogenative silylation (scheme 3b). As
6 4 2
SiMe(o-C H SMe) spanning one of the octahedron faces. The
triphenylphosphine ligand is now located trans to the silyl
fragment, while the two hydride ligands are opposite the thioether
groups. This disposition could be explained due to the trans
influence of the silyl and the hydride groups. In the 1H NMR
spectra of complex 4, the signal corresponding to the hydrido is
observed at -14.25 ppm (d, JP-H = 14.8 Hz), Other three, integral
1
6c
expected, 6 consists of a 3:1 mixture of E/Z isomers.
In all
cases the silylation products obtained were selectively anti-
Markovnikov. The efficiency of cationic complexes as precatalysts
was proved higher as neutral Ir(III) complex 2 was reached only
3
0% conversion (Table 1, entry 2), with dehydrogenative silylation
products being also the main compounds among the final mixture.
The difference in the labile nature of the chloride and the
tetrahydrofuran can explain the decreased conversion on going
from 4 to 2. Complex 3 was inactive for these catalyses (Table 1,
entry 3). We propose that the presence of a second hydride
instead of chloride or tetrahydrofuran would block the possibility
3
H methyl signals at 3.30, 2.60, and -0.06 ppm are assigned to
the non-equivalent SMe units and the SiMe group in the molecule,
respectively. Furthermore, the observation of two signals at 3.57
and 1.70 ppm suggest the presence of coordinated
tetrahydrofuran. Formation of 4 is also supported by ESI-MS
spectroscopy that shows a molecular ion at m/z = 745.12 (calcd.
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of generating a vacant coordination site on the metal centre and
thus explain the lack or reactivity of 3.
[
a,b]
Table 2. Hydrosilylation of alkenes with Et
3
SiH using complexes 1 and 4.
Scheme 3. a) Tandem isomerization-hydrosilylation of trans-2-octene with
Et
3
SiH using catalyst 1. b) Tandem isomerization-dehydrogenative silylation of
SiH using catalysts 1 and 4.
trans-2-octene with Et
3
5
5
76%(>99)
62%(>99)
60%(95)
90%(93)
6(E+Z) 73%(59)
6(E+Z) 70%(56)
6(E+Z) 67%(57)
6(E+Z) 71%(50)
[
a]
3
Table 1. Hydrosilylation of trans-2-octene with Et SiH.
5
5
[
b]
Entry
Catalyst
Temperature (ºC)
Conversion (%)
[
c]
d]
e]
[
c]
7 73%(98)
8(E+Z) 69%(36)
1
2
3
4
1
2
3
4
r.t.
50
50
50
76
30
[
[
7
67%(>99)
8(E+Z) 60%(50)
8(E+Z) 63%(47)
No reaction
[
d]
7 83%(>98)
73
[
a] Reaction conditions: alkene (0.25 mmol) and Et
3
SiH (0.25 mmol) with 1
mol % of catalyst solvent-free at room temperature, after 12 hours. [b]
1
Conversions determined by
H NMR by silane remaining. [c] >99%
9
92%(98)
10(E+Z) 79%(85)
selectivity to terminal silane. [d] 60% selectivity to allyl silane.
–
1
1 53%(89)
On view of these results a further study with other internal and
terminal alkenes was carried out using cationic 1 and 4 catalysts
[f]
1
2 91%(>99)
12 89%(>99)
(
Table 2). For catalyst 1, an extraordinary selectivity to linear
alkylsilanes was obtained, the minor products being the
corresponding unsaturated dehydrogenative silylation products.
Trans-3- and trans-4-octene, which have remote double bonds,
also yielded products silylated in the terminal position selectively,
with remarkable conversion of 62% and 60% respectively (Table
1
3 68%(82)
14 50%(68)
2
, product 5). Trans-2 and trans-3-hexene yielded the hexylsilane
1
1
5 29%(>99)
15 40%(>99)
(
Table 2, product 7) to reach conversions of 73% and 67%
respectively, similar to those observed for trans-2-octene. The
highest conversion percentages (90% and 83%) were reached
with terminal alkene isomers such as 1-octene and 1-hexene, to
yield the corresponding alkylsilane (products 5 and 7). Tert-
butylethylene (tbe) and allyltrimethylsilane, both terminal alkenes,
led selectively to the formation of 12 and 9, respectively, with
almost complete conversion, while 4-bromo-1-butene reached
1
6 54%(>99)
6 23%(>99)
[
3
a] Reaction conditions: alkene (0.25 mmol) and Et SiH (0.25 mmol) with 1
mol % of complex 1 or 4 solvent-free at room temperature (1) or 50 ºC (4)
1
after 12h. [b] Conversions determined by H NMR by silane remaining using
1,2-dichloroethane as internal standard. Selectivity determined by H NMR
1
5
3% conversion with lower selectivity to 11 after 12 hours. The
after work-up of the reaction (value indicated on parenthesis). [c] 43%
selectivity to dehydrogenative silylation products. [d] 66% selectivity to
dehydrogenative silylation products. [e] 61% selectivity to dehydrogenative
silylation products. [f] Experiment carried out at room temperature.
reaction with styrene afforded 68% conversion under the same
reaction conditions, with 82% selectivity to the linear
hydrosilylation product 13, whereas styrene derivatives such as
α-methylstyrene and 4-chloro-α-methylstyrene gave 29% and
The catalytic activity of complex 4 in dehydrogenative silylation of
2
3% conversion to 15 and 16, respectively, with excellent linear
3
these alkenes with Et SiH was also tested (Table 2). Octene
selectivity.
isomers reached similar conversions of 67-73%, the major
product being the allylic silylated compound 6. The presence of
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vinylsilane products in these catalytic reactions was less than 1%.
When using hexenes, similar conversions are attained, however
the ratio of vinylsilanes increases, to reach 7%, 16% and 14% of
the product mixture in the reaction of trans-3-, trans-2- and 1-
hexene, respectively (See supporting information). Longer chain
in octanes might explain the higher allylsilane percentage, as the
steric repulsion would lead towards selective β-hydride
[1]
a) I. Fleming In Comprehensive Organic Chemistry II; D. Burton, W. D.
Ollis, Eds.; Pergamon Press: Oxford, U.K. 1979; p 577. b) D. R. Thomas
Comprehensive Organometallic Chemistry; W. W. Abel, F. G. A. Stone,
G. Wilkinson, Eds.; Pergamon Press, Oxford, U.K. 1995; p 114.
a) J. Michl, Chem. Rev. 1995, 95, 1135. b) S. Bracegirdle, E. A.
Anderson, Chem. Soc. Rev. 2010, 39, 4114.
[
[
2]
3]
a) I. Ojima, In The Chemistry of Organic Silicon Compounds; S. Patai, Z.
Rappoport, Eds.; Wiley-Interscience: New York, 1989; Vol. 2, p 1479. b)
T. Nakajima, S. Shimada, RSC Adv. 2015, 5, 20603.
[
16c]
elimination in the reaction intermediate.
Higher amounts of
dehydrogenative silylation products were reached, from which 8
was the main species. Allyltrimethylsilane afforded selective 79%
conversion to 10, whereas 4-bromo-1-butene underwent very
poor reaction. The formation of allylsilane products in the
dehydrogenative silylation of styrene, α-methylstyrene, 4-chloro-
α-methylstyrene and tbe is not possible, for they can only yield the
vinylsilane species. All of these alkenes exhibit very high
selectivity towards the hydrosilylated product except styrene, in
which vinylsilane 14 is present in a 68% of the silylated product.
This could once again be explained by steric repulsion caused by
methyl groups in α-methylstyrene, 4-chloro-α-methylstyrene, and
tbe when the silylated product is coordinated to Ir that make β-
[4]
J. L. Speier, J. A. Webster, G. H. Barnes, J. Am. Chem. Soc. 1957, 79,
9
74.
[
[
5]
6]
P. B. Hitchcock, F. M. Lappert, N. J. W. Warhurst, Angew. Chem. Int.
Ed. 1991, 30, 438; Angew. Chem. 1991, 103, 439.
a) K. Hirano, H. Yorimitsu, K. Oshima, J. Am. Chem. Soc. 2007, 129,
6
9
094. b) J. C. Mitchener, M. S. Wrighton, J. Am. Chem. Soc. 1981, 103,
75. c) S. C. Bart, E. Lobkovsky, P. J. Chirik, J. Am. Chem. Soc. 2004,
126, 13794. d) Z. Mo, J. Xiao, Y. Gao, L. Deng, J. Am. Chem. Soc. 2014,
136, 17414. e) C. Chen, M. B. Hecht, A. Kavara, W. W. Brennessel, B.
Q. Mercado, D. J. Weix, P. L. Holland, J. Am. Chem. Soc. 2015, 137,
1
3244.
[
[
7]
8]
B. Marciniec, H. Maciejewski, C. Pietraszuk, P. Pawluc, Hydrosilylation:
A Comprehensive Review on Recent Advances; Springer: London, 2009;
p VII-XII.
[
16c]
hydride elimination unfavourable.
Hydrosilylation of tbe
a) G. R. Jones, Y. Landais, Tetrahedron, 1996, 52, 7599. b) Y. Hatanaka
T. Hiyama, J. Org. Chem. 1988, 53, 918. c) A. Hosomi, H. Sakurai,
Tetrahedron Lett. 1976, 1295.
successfully yielded linear product 12 to reach 89% of conversion.
Notably, the hydrosilylation products of α-methylstyrene and 4-
chloro-α-methylstyrene with Et
3
SiH (15 and 16) were obtained in
[9]
a) B. Marciniec, Coord. Chem. Rev. 2005, 249, 2374. b) M. Lapointe, F.
C. Rix, M. Brookhart, J. Am. Chem. Soc. 1997, 119, 906.
a) Y. Hori, T. Mitsudo, Y. Watanabe, Bull. Chem. Soc. Jpn. 1988, 61,
higher yield (54%) when using the iridium(III) catalyst 4 than when
using the rhodium(III) analogue. In alkene dehydrogenative
silylation reactions, the use of a sacrificial hydrogen acceptor
[
10]
3
011. b)M. P. Doyle, G. A. Devora, A. Nefedov, K. G. High,
[
10-13]
Organometallics, 1992, 11, 549. c) A. Millan, E. Towns, P. M. Maitlis, J.
Chem. Soc., Chem. Commun. 1981, 673. d) A. Bokka, J. Jeon, Org. Lett.
(
SHA) is usually necessary.
The SHA can be the same
alkene that reacts with hydrogen to form an alkane. In our case,
alkane is not observed upon completion of the reaction. This fact
shows that under our conditions, the use of a SHA is no necessary
2
016, 18, 5324.
[
11] R. N. Naumov, M. Itazaki, M. Kamitani, H Nakazawa, J. Am. Chem. Soc.
2012, 134, 804.
1
0b
as has been previously reported for other catalytic systems.
In
[12] J. Gu, C. Cai, Chem. Commun. 2016, 52, 10779.
order to check this, the catalytic dehydrogenative silylation was
carried out adding an extra equivalent of trans-2-octene (SHA). At
the end of this reaction the formation of triethyl(2-octenyl)silane
was equal and octane was not observed (Figure S.67. Supp. Info.).
[13] a)D. C. Apple, K. A. Brady, J. M. Chance, N. E. Heard, T. A. Nile, J. Mol.
Catal. 1985, 29, 55. b) M. A. Fernandez, L. A. Oro, J. Mol. Catal. 1986,
3
7, 151. c) D. Wechsler, A. Myers, R. McDonald, M. J. Ferguson, M.
Stradiotto, Inorg. Chem. 2006, 45, 4562. d) E. Calimano, T. D. Tilley, J.
Am. Chem. Soc. 2009, 131, 11161. e) C. Cheng, E. M. Simmons, J. F.
Hartwig, Angew. Chem. Int. Ed. 2013, 52, 8984; Angew. Chem. 2013,
In conclusion, an unsaturated silyl-hydrido-Rh(III) complex
containing a Si,S,S-terdentate ligand is able to catalyze solvent
free tandem isomerization-hydrosilylation of internal alkenes at
room temperature to yield linear silanes. The synthesis of an
analogue novel iridium(III) complex was also reported. This silyl-
hydrido-Ir(III) compound is active in one of the few examples of
catalytic tandem isomerization-dehydrogenative silylation of
alkenes.
1
25, 9154. f) J. A. Muchnij, F. B. Kwaramba, R. J. Rahaim, Org. Lett.
2014, 16, 1330.
[14] X. Jia, Z. Huang, Nat. Chem. 2016, 8, 157.
[15] a) I. Buslov, J. Becouse, S. Mazza, M. Montandon-Clerc, X. Hu, Angew.
Chem. Int. Ed. 2015, 54, 14523; Angew. Chem. 2015, 127, 14731. b) V.
Srinivas, Y. Nakajima, W. Ando, K. Sato, S. Shimada, S. Catal. Sci.
Tecnol. 2015, 5, 2081.
[
16] a) A. Vasseur, J. Bruffaerts, I. Marek, Nat. Chem. 2016, 8, 209. b) D.
Noda, A. Tahara, Y. Sunada, H. Nagashima, J. Am. Chem. Soc. 2016,
1
38, 2480. c) C. C. H. Atienza, T. Diao, K. J. Weller, S. A. Nye, K. L.
Lewis, J. G. P. Delis, J. L. Boyer, A. K. Roy, P. J. Chirik, J. Am. Chem.
Soc. 2014, 136, 12108.
Acknowledgements ((optional))
[
17] I. Buslov, F. Song, X. Hu, Angew. Chem. Int. Ed. 2016, 55, 12295; Angew.
Chem. 2016, 128, 12483.
Financial support by Ministerio de Economía y Competitividad
[
18] S. Azpeitia, M. A. Garralda, M. A. Huertos, ChemCatChem. 2017, 9,
(
CTQ2015-65268-C2-2-P
and
CTQ2015-65268-C2-1-P),
1
901.
Gobierno Vasco and Universidad del País Vasco (UPV/EHU) is
gratefully acknowledged.
[19]
S. Azpeitia, B. Fernandez, M. A. Garralda, M. A. Huertos, Eur. J. Inorg.
Chem. 2016, 2891.
[
20] CCDC 1554040 (2), 1554041 (3) contain the supplementary
crystallographic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre.
Keywords: Remote Alkenes • Hydrosilylation • Dehydrogenative
Silylation • Rhodium • Iridium
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Entry for the Table of Contents (Please choose one layout)
Layout 2:
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Susan Azpeitia, Antonio Rodriguez-
Dieguez, María A. Garralda and Miguel
A. Huertos*
Page No. – Page No.
Rh vs Ir: An unsaturated
16e
From Remote Alkenes to Linear
Silanes or Allyl Silanes Depending on
the Metal Centre
hydrido-silyl-Rh(III) complex is an efficient catalyst for a tandem catalytic alkene
isomerization-hydrosilylation reaction while its analogue made of iridium is useful to
synthesize allyl silanes from remote alkenes.
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