Rhodium(I) N-heterocyclic carbene complexes as catalysts for the hydrosilylation of aromatic ketones with triethylsilane

Article abstract of DOI:10.1016/j.ica.2017.07.055

New rhodium(I) N-heterocyclic carbene complexes were synthesized in good yields by the reactions of rhodium dimer [Rh(OMe)COD]₂ with two equivalent of 1,3-dialkylimidazolinium chloride salts in tetrahydrofuran. All of the complexes were charact

Full text of DOI:10.1016/j.ica.2017.07.055

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Research paper
Rhodium(I) N-heterocyclic carbene complexes as catalysts for the hydrosilyla-
tion of aromatic ketones with triethylsilane
Beyhan Yiğit, Murat Yiğit, İsmail Özdemir
PII:
S0020-1693(17)30054-3
http://dx.doi.org/10.1016/j.ica.2017.07.055
ICA 17778
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Please cite this article as: B. Yiğit, M. Yiğit, I. Özdemir, Rhodium(I) N-heterocyclic carbene complexes as catalysts
for the hydrosilylation of aromatic ketones with triethylsilane, Inorganica Chimica Acta (2017), doi: http://
dx.doi.org/10.1016/j.ica.2017.07.055
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Rhodium(I) N-heterocyclic carbene complexes as catalysts for the hydrosilylation of
aromatic ketones with triethylsilane
Beyhan Yiğit1*, Murat Yiğit1, İsmail Özdemir2,3
1
Department of Chemistry, Faculty of Science and Art, Adıyaman University, 02040
Adıyaman, Turkey
2
Department of Chemistry, Faculty of Science and Art, Inönü University, 44280 Malatya,
Turkey
3Catalysis Research and Application Center, Inönü University, 44280 Malatya, Turkey
Abstract
New rhodium(I) N-heterocyclic carbene complexes were synthesized in good yields by the
reactions of rhodium dimer [Rh(OMe)COD]2 with two equivalent of 1,3-
dialkylimidazolinium chloride salts in tetrahydrofuran. All of the complexes were
characterized using elemental analysis, 1H NMR and 13C NMR spectroscopy. These
complexes were used as catalysts in the hydrosilylation of acetophenone derivatives with
o
triethylsilane at 80 C for 1h. These Rh(I)-NHC complexes showed the good catalytic
performance for the hydrosilylation of acetophenone derivatives and the corresponding
hydrosilylation products were obtained in moderate to good yields by using 1 mol % of the
rhodium complex.
1. Introduction
In recent years, N-heterocyclic carbenes have risen to an important position among the
ligands for transitions metals due to their unique properties and numerous applications [1-4].
N-Heterocyclic carbenes are strong σ-donating and weak π-accepting ligands. These carbene
ligands interact with metal centers and produce stable metal-NHC complexes with strong
covalent bonds. This strong metal-carbon bond avoids the decomposition of NHC complexes
during the course of catalytic reactions [5-7]. Additionally, the NHC ligands can be easily
modified by changing the substituents on the nitrogen atoms or the carbene ring, which
provides various ligands for organometallic chemistry [8-10]. A variety metal complexes of
N-heterocyclic carbenes have been synthesized and used as catalysts for many chemical
transformations [11-21].

The transition metal-catalyzed addition of hydrosilane compounds to carbon-carbon
and carbon heteroatom multiple bonds as known hydrosilylation is one of the most important
methods for the preparation of organosilicon compounds, which are valuable synthetic
intermediates especially for the silicon industry [22-24]. Hydrosilylation of carbon heteroatom
multiple bonds is an useful alternative to other reduction methods such as hydrogenation,
transfer hydrogenation as well as reduction with hydride reagents due to its operational
simplicity besides atom-economy [25-28]. This reduction reaction is two-step process
involving the catalytic hydrosilylation of carbon heteroatom multiple bonds and subsequent
hydrolysis of the resulting hydrosilylation products to give an alcohol or an amine [29-31]. A
number of transition metal-based catalyst systems have been developed for both asymmetric
[32-37] and nonasymmetric hydrosilylation reactions [38-48]. In particular, rhodium
complexes have displayed high catalytic activity in the hydrosilylation of carbonyl
compounds and olefins [49-53]. In 1977, Hill and Nile reported the first use of N-heterocyclic
carbene rhodium (COD) complexes as hydrosilylation catalysts for a variety of organic
substrates [54]. Later, Lappert and Maskell have reported the hydrosilylation of acetophenone
with triethylsilane using rhodium(I) N-heterocyclic carbene complexes as catalyst [55]. The
first asymmetric hydrosilylation of acetophenone with diphenylsilane using chiral rhodium-N-
heterocyclic carbene complexes was achieved by Herrmann and co-workers [56]. After these
reports, a number of transition metal complexes containing N-heterocyclic carbene ligands
have been used as hydrosilylation catalysts [57-72].
The synthesis of N-heterocyclic carbenes mainly depends on the deprotonation of the
imidazolium, benzimidazolium and imidazolinium salts. Therefore, synthesis of these salts is
important. Aromatic aldehydes have been widely used as starting materials for the synthesis
of the azolium salts, but use of aromatic ketones were limited due to probably low reactivity
toward nucleophiles [73, 74]. Herein, we wish to report the the synthesis and characterization
of new rhodium COD complexes with imidazolin-2-ylidene ligand derived from the
imidazolinium salts as NHC precursors which were prepared starting from aromatic ketones
and use of rhodium complexes as catalysts for the hydrosilylation of acetophenone derivatives
with triethylsilane.
2. Experimental
2.1. Materials and methods

All reactions for the preparation of the rhodium(I)-NHC complexes were carried out under
argon in flame-dried glassware using standard Schlenk techniques. The imidazolinium salts
were prepared according to ref. [73]. The solvents used were purified by distillation over the
drying agents indicated and were transferred under Ar: THF, Et2O (Na/K alloy), CH2Cl2
(P4H10), hexane, toluene (Na). All reagents were purchased from Sigma-Aldrich, Merck and
1
Fluka. All H- and 13C-NMR were recorded in CDCI3 using a Bruker AC300P FT
spectrometer operating at 300.13 MHz (1H) or 75.47 MHz (13C). Chemical shifts () are given
in ppm relative to TMS, coupling constants (J) in hertz. FT-IR spectra were recorded as KBr
pellets in the range 400-4000 cm-1 on a Mattson 1000 spectrophotometer (wavenumbers, cm-
1). GC were measured by GC-FID on a Agilent 6890N gas chromatograph equipped with an
HP-5 column of 30 m length, 0.32 mm diameter and 0.25 m film thickness. Melting points
were measured in open capillary tubes with an Electrothermal-9200 melting point apparatus
and uncorrected. Elemental analyses were performed at Inönü University research center.
2.2. Synthesis of imidazolinium salts, 1
A mixture of 1,2-bis(alkylamino)ethane (4.2 mmol), NH4Cl (4.2 mmol) and triethyl

orthoformate (10 mL) was heated for 12 h at 110 C. Upon cooling to room temperature,
colorless crystals were obtained. These were filtered off, washed with diethyl ether (3 × 15
mL) and dried under vacuum. The crude product was recrystallized from EtOH / Et2O.
2.2.1. 1,3-Di[1-(3,4,5-trimethoxyphenyl)ethyl]imidazolinium chloride, 1d
Yield: 1.75 g, 84%, m.p. 206-208 oC. IR, υ: 1633 cm-1 (NCN). 1H NMR (DMSO-d6) δ:
1.72 (d, 6H, J = 8 Hz, CH(CH3)C6H2(OMe)-3,4,5); 3.37 and 3.65 (m, 4H, NCH2CH2N); 3.79
(s, 6H, CH(CH3)C6H2(OMe)-3,4,5); 3.80 (s, 12H, CH(CH3)C6H2(OMe)-3,4,5); 4.88-4.93 (m ,
2H, CH(CH3)C6H2(OMe)-3,4,5); 6.83 and 6.84 (s, 4H, CH(CH3)C6H2(OMe)-3,4,5);  9.38
(s, 1H, NCHN). 13C NMR (DMSO-d6) δ: 19.3 and 19.6 (CH(CH3)C6H2(OMe)-3,4,5); 46.5
(NCH2CH2N); 55.5 and 55.8 CH(CH3)C6H2(OMe)-3,4,5); 60.3 (CH(CH3)C6H2(OMe)-3,4,5);
104.9; 105.0; 105.1; 134.8; 134.9; 137.7; 153.5; 155.6 and 155.9 (Ar-C); 156.1 (NCHN).
Anal. Calcd for C25H35N2O6Cl: C, 60.66; H, 7.08; N, 5.66. Found: C, 60.82; H, 7.24; N, 5.74.
2.3. Synthesis of rhodium(I)-NHC complexes, 2
To a solution of 1,3-dialkylimidazolinium chloride (0.42 mmol) in THF (10 mL) was added
rhodium dimer [Rh(OMe)COD]2 (0.21 mmol) and the resulting mixture was stirred at reflux
for 12 h. After removal of the solvent, the residue was washed with diethylether (10 mL) and

dried under vacuum. The crude product was recrystallized from CH2Cl2/Et2O, and yellow-
orange crystals were obtained.
2.3.1. Chloro(4-1,5-cyclooctadiene)bis[1,3-dibenzhydrylimidazolin-2-ylidene]rhodium(I),2a
o
1
Yield: 0.21 g, 78%, m.p. 230-232 C. IR, υ: 1493 cm-1 (NCN). H NMR (CDCI3) δ:
3.08-3.11 (m, 4H, NCH2CH2N); 7.31-7.48 (m, 20H, Ar-H); 8.15 (s, 2H, CH(C6H5)2); 3.60-
3.66 (m, 2H, COD-CH); 5.08-5.10 (m, 2H, COD-CH); 1.74-1.82 (m, 4H, COD-CH2); 2.22-
2.26 (m, 4H, COD-CH2). 13C NMR (CDCI3) δ: 46.0 (NCH2CH2N); 66.5 (CH(C6H5)2); 127.2,
127.4, 127.7, 128.4, 128.5, 130.1, 139.0 and 140.8 (Ar-C); 69.4 (d, JRh-C = 14.3 Hz, COD-
CH); 99.1 (d, JRh-C = 6.6 Hz, COD-CH); 28.5 (COD-CH2); 32.4 (COD-CH2); 215.4 (d, JRh-
Carbene = 47.5 Hz, Ccarbene). Anal. Calcd for C37H38N2ClRh: C, 68.46; H, 5.86; N, 4.32. Found:
C, 68.51; H, 5.81; N, 4.38.
2.3.2.
Chloro(4-1,5-cyclooctadiene)bis[1,3-di(1-phenylethyl)imidazolin-2-
ylidene]rhodium(I),2b
o
1
Yield: 0.18 g, 82%, m.p. 167-169 C. IR, υ: 1483 cm-1 (NCN). H NMR (CDCI3) δ:
1.75-1.81 (m, 6H, CH(CH3)C6H5); 3.21-3,35 (m, 4H, NCH2CH2N); 6.72 (quart., 2H, J = 6.9
Hz, CH(CH3)C6H5); 7.28 and 7.43 (m, 10H, Ar-H); 3.53-3.59 (m, 2H, COD-CH); 5.04-5.11
13
(m, 2H, COD-CH); 1.89-1.94 (m, 4H, COD-CH2); 2.31-2.39 (m, 4H, COD-CH2). C NMR
(CDCI3) δ: 17.9 (CH(CH3)C6H5); 43.2 (NCH2CH2N); 57.7 (CH(CH3)C6H5); 126.7, 126.8,
127.3, 127.4, 127.5, 127.9, 128.4, 128.6, 128.7, 129.1, 140.9 and 141.4 (Ar-C); 68.2 (d, JRh-C
= 14.6 Hz, COD-CH); 99.0 (d, JRh-C = 6.2 Hz, COD-CH); 28.6 (COD-CH2); 32.7 (COD-CH2);
211.6 (d, JRh-Carbene = 46.5 Hz, Ccarbene). Anal. Calcd for C27H34N2ClRh: C, 61.77; H, 6.48; N,
5.34. Found: C,61.83; H, 6.41; N, 5.38.
2.3.3.
Chloro(4-1,5-cyclooctadiene)bis[1,3-di(1-(4-methoxyphenyl)ethyl)imidazolin-2-
ylidene]rhodium(I), 2c
o
1
Yield: 0.18 g, 75%, m.p. 216-218 C. IR, υ: 1510 cm-1 (NCN). H NMR (CDCI3) δ:
1.70 and 1.74 (d, 6H, J = 6.9 Hz, CH(CH3)C6H4(OMe)-4); 3.13-3,33 (m, 4H, NCH2CH2N);
3.81 and 3.84 (s, 6H, CH(CH3)C6H4(OMe)-4); 6.63 and 6.73 (quart., 2H, J = 6.9 Hz,
CH(CH3)C6H4(OMe)-4); 6.91-7.30 (m, 8H, CH(CH3)C6H4(OMe)-4); 3.48-3.59 (m, 2H, COD-
CH); 5.04-5.11 (m, 2H, COD-CH); 1.88-1.97 (m, 4H, COD-CH2); 2.29-2.39 (m, 4H, COD-
CH2). 13C NMR (CDCI3) δ: 17.4 and 17.9 (CH(CH3)C6H4(OMe)-4); 42.3 and 42.9

(NCH2CH2N); 55.25; 55.32 CH(CH3)C6H4(OMe)-4); 56.3 and 57.3 (CH(CH3)C6H4(OMe)-4);
113.7, 113.9, 127.9, 129.2, 131.5, 133.3, 158.7 and 158.9 (Ar-C); 67.6 and 68.6 (d, JRh-C
=
14.3 Hz, COD-CH); 98.9 (d, JRh-C = 6.0 Hz, COD-CH); 28.6 (COD-CH2); 32.7 and 32.9
(COD-CH2); 210.6 (d, JRh-Carbene = 46.5 Hz, Ccarbene). Anal. Calcd for C29H38N2O2ClRh: C,
59.54; H, 6.50; N, 4.79. Found: C, 59.59; H, 6.58; N, 4.85.
2.3.4. Chloro(4-1,5-cyclooctadiene)bis[1,3-di(1-(3,4,5-trimethoxyphenyl)ethyl)imidazolin-2-
ylidene]rhodium(I), 2d
o
1
Yield: 0.22 g, 72%, m.p. 203-205 C. IR, υ: 1508 cm-1 (NCN). H NMR (CDCI3) δ:
1.71 (d, 6H, J = 6.9 Hz, CH(CH3)C6H2(OMe)-3,4,5); 2.92 and 3,28 (t, 4H, J = 3.6 Hz,
NCH2CH2N); 3.85 (s, 6H, CH(CH3)C6H2(OMe)-3,4,5) and 3.89 (s, 12H,
CH(CH3)C6H2(OMe)-3,4,5); 6.71 (quart., 2H, J = 7.2 Hz, CH(CH3)C6H2(OMe)-3,4,5); 7.05
(s, 4H, CH(CH3)C6H2(OMe)-3,4,5); 3.63-3.65 (m, 2H, COD-CH); 5.06-5.08 (m, 2H, COD-
CH); 1.97-2.03 (m, 4H, COD-CH2); 2.39-2.46 (m, 4H, COD-CH2). 13C NMR (CDCI3) δ: 17.3
(CH(CH3)C6H2(OMe)-3,4,5); 42.3 (NCH2CH2N); 56.6 and 56.7 CH(CH3)C6H2(OMe)-3,4,5);
60.7 (CH(CH3)C6H2(OMe)-3,4,5); 105.6, 135.0, 137.4, 153.1, 153.1 and 153.3 (Ar-C); 68.5
(d, JRh-C = 13.5 Hz, COD-CH); 98.1 (d, JRh-C = 6.0 Hz, COD-CH); 28.6 (COD-CH2); 32.9
(COD-CH2); 209.4 (d, JRh-Carbene = 46.5 Hz, Ccarbene). Anal. Calcd for C33H46N2O6ClRh: C,
56.21; H, 6.53; N, 3.97. Found: C, 56.26; H, 6.48; N, 3.91.
2.4. General procedure for the the hydrosilylation reactions
The acetophenone derivative (1 mmol), triethylsilane (1.25 mmol) and rhodium complex
(0.01 mmol) were introduced in a Schlenk tube equipped with a magnetic stirring bar. The
Schlenk tube was placed in a preheated oil bath at 80 oC, the reaction mixture was stirred for 1
h. Then, the reaction mixture was cooled to ambient temperature, and purified by flash
chromatography using a hexane/ ethyl acetate (10/1) mixture as the eluent.
3. Results and discussion
3.1. Synthesis of Rh(I)-NHC complexes
Various synthesis routes are available to prepare N-heterocyclic carbene rhodium
(COD) complexes include (i) reaction of a free carbene with dimeric precursor
[Rh(COD)Cl2]2 [75], (ii) in situ deprotonation of azolium salts with a rhodium dimer
[Rh(OMe)COD]2 [76], (iii) reaction of a electron-rich enetetramines with [Rh(COD)Cl2]2

under C=C bond cleavage [77], (iv) transfer of the carbene unit from silver(I)-NHC complex
to rhodium metal [78]. We chose the second preparation pathway for the synthesis of Rh(I)-
NHC complexes. The advantage of this route is that no pregeneration of the free carbene is
necessary and the methoxy ligands are protonated to give methanol upon reaction with the
imidazolium salt. Rhodium N-heterocyclic carbene complexes 2a-d were prepared by
treatment of rhodium dimer [Rh(OMe)COD]2 with two equivalent of 1,3-
dialkylimidazolinium chloride salts in tetrahydrofuran under reflux. The complexes 2a-d were
obtained as yellow-orange crystalline solids in 72-82% yields.
N
Rh
N
Cl
2a
OMe
OMe
R
OMe
N
+) Cl-
N
N
N
N
N
Rh
Cl
Rh
Cl
R
1
+
OMe
OMe
[Rh(OMe)COD]2
2d
2b
OMe
OMe
N
Rh
N
Cl
2c
OMe

Scheme 1. The synthesis of rhodium(I)-NHC complexes.
The new Rh complexes are very stable in the solid state and have been characterized
13
by 1H and C- NMR spectroscopy, FTIR and elemental analysis. They show a characteristic
υ(NCN) band at 1493, 1483, 1510 and 1508 cm-1 for 2a, 2b, 2c and 2d, respectively. The
formation of Rh(I)-NHC complexes 2a-d were confirmed by the loss of the resonance signals
of perhydrobenzimidazolium C2 proton at 8.24 ppm for 1a, 10.65 ppm for 1b, 10.60 ppm for
1
1c and 9.38 ppm for 1d in the H NMR spectra and C2 carbon at 158.6, 156.8, 159.8 and
13
13
155.9 ppm respectively for 1a-d in C NMR spectra. The C- NMR chemical shifts, which
provide a useful diagnostic tool for metal carbene complexes, show that Ccarbene is
substantially deshielded. The resonance of the carbene carbon of rhodium complexes was
observed as a doublet at 215.4 (2a), 211.6 (2b), 210.6 (2c), 209.4 (2d) ppm and coupling
constants J(103Rh-13C) were 47.5 (2a), 46.5 (2b, 2c, 2d) Hz and these values were similar to
those found for other rhodium(I) carbene complexes [50, 64]. The results obtained from the
elemental analysis of the complexes 2a-d are in agreement with the theoretical requirements
of their structures.
3.2. Catalytic studies: Hydrosilylation of acetophenone derivatives with triethylsilane
Transition metal-catalyzed hydrosilylation of carbonyl compounds has attracted much
attention in the last years as it is an efficient synthetic alternative to other reduction methods
for the synthesis of alcohols. A number of transition metal complexes have displayed high
catalytic activity for the hydrosilylation of carbonyl compounds. Among them, rhodium
complexes are highly active catalysts for this reactions. The catalytic activities of the new
Rh(I)-NHC complexes were evaluated on hydrosilylation of acetophenone derivatives. Based
on our previous results, in this study, the catalytic experiments were carried out using 1 mmol
o
ketone, 1.25 mmol triethylsilane and 0.01 mmol 2a-d at 80 C for 1 h. No reaction between
acetophenone derivatives with triethylsilane was observed in the absence of the Rh(I)-NHC
complex under this reaction conditions. The conversions of the products were screened by GC
analysis and results were summarized in Table 1. Under these reaction conditions,
triethylsilane were reacted with acetophenone and acetophenone derivatives bearing electron-
donating or electron-withdrawing groups at the para or ortho position to produce the
corresponding silylethers in moderate to good yields (Table 1).

Table 1. Hydrosilylation of acetophenone derivatives with triethylsilane.a
OSiEt3
O
Rh-NHC
+
HSiEt3
C H
C
CH3
R
R
CH3
3-6
7
8-11
Yield % b
Ketone
Entry
Rh-NHC
Product
1
2
3
4
5
6
7
8
84
88
89
91
85
87
86
93
2a
2b
2c
2d
2a
2b
2c
2d
OSiEt3
O
C
CH3
C H
CH3
3
8
O
C
OSiEt3
CH3
C H
CH3
OCH3
OCH3
9
4
9
91
90
94
96
79
81
83
86
2a
2b
2c
2d
2a
2b
2c
2d
O
C
OSiEt3
10
11
12
13
14
15
16
CH3
C H
CH3
10
H3CO
H3CO
5
O
C
OSiEt3
Cl
CH3
Cl
C H
CH3
11
6
aReaction conditions: Rh-NHC (0.01 mmol), acetophenone derivative (1.00 mmol),
triethylsilane (1.25 mmol), 1 h, 80 oC. bGC yields using dodecane as internal standard in
an average of two runs and stucture of compound was checked by NMR.

Initially, the reaction of acetophenone (3) with triethylsilane (7) was examined in the presence
of complexes 2a-d as catalysts. The hydrosilylation products (8) were obtained in 84-91%
yields for all four catalysts (Table 1, entries 1-4). Then, 2-methoxyacetophenone (4), 3-
methoxyacetophenone (5) and 4-chloroacetophenone (6) were reacted with triethylsilane in
the presence of complexes 2a-d under the same reaction conditions (Table 1, entries 5-16).
When the 3-methoxyacetophenone (5) was used as the substrate, the best yields (94% and
96%) were achieved with catalysts 2c and 2d to give corresponding silylethers (10). However,
in case of 4-chloroacetophenone (6), silylethers (11) were obtained in slightly lower yields
(79-86%). Among the tested complexes, rhodium complexes (2c, 2d) with methoxy
substituents on phenyl group exhibited higher catalytic activities compared to those bearing
unsubstituted phenyl group (2a, 2b) for the hydrosilylation of acetophenone derivatives and
high yields were obtained with complex 2c. When compared with the related literature in the
hydrosilylation of acetophenone derivatives with triethylsilane, our complexes exhibit similar
or better catalytic activity than the other Rh(I) systems bearing NHC ligands [50, 55, 79].
4. Conclusion
In summary, The rhodium(I)-NHC complexes 2a-d have been easily prepared in good
yields by the reactions of rhodium dimer [Rh(OMe)COD]2 with two equivalent of 1,3-
dialkylimidazolinium chloride salts in tetrahydrofuran. The catalytic activity of these
complexes was investigated in the hydrosilylation of acetophenone derivatives with
triethylsilane. The hydrosilylation reactions were performed in solvent free conditions for 1 h
o
at 80 C using 1 mol% of the complexes 2a-d, high yields were obtained. These rhodium
complexes demonstrated excellent catalytic activity in the hydrosilylation of acetophenone
derivatives. Among the tested complexes, the rhodium complexes (2c, d) containing NHC
ligands with methoxy groups exhibited better catalytic activity.
Acknowledgements
We thank the Adıyaman University Research Fund (FEFMAP/2015-0004) for
financial support of this work.
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 The new Rh(I)-NHC complexes were prepared.
1
 These complexes were characterized by elemental analysis, IR, H, 13C NMR
pectroscopy.
 The new RhI complexes were tested as catalysts in the hydrosilylation of
acetophenone derivatives.

Rhodium(I) N-heterocyclic carbene complexes as catalysts for the hydrosilylation of
aromatic ketones with triethylsilane
Beyhan Yiğit, Murat Yiğit, İsmail Özdemir
New rhodium(I) N-heterocyclic carbene complexes were synthesized and used as catalysts in
the hydrosilylation of acetophenone derivatives with triethylsilane. These Rh(I)-NHC
complexes showed the good catalytic performance for the hydrosilylation of acetophenone
derivatives and the corresponding hydrosilylation products were obtained in moderate to good
yields.
OSiEt3
C H
CH3
O
Rh-NHC
+
HSiEt3
C CH3
R
R