Ruthenacyclic Carbamoyl Complexes: Highly Efficient Catalysts for Organosilane Hydrolysis

Article abstract of DOI:10.1002/ejic.201801012

The ruthenacyclic carbamoyl complexes [RuX{2-NHC(O)C₅H₃NR}(CO)₂(NCMe)] (R = H and Me; X = Br and SC₆H₃-o,o-Me₂) are excellent catalysts for the hydrolysis of organosilanes, particularly towards primary silanes, generating hydrogen under ambient conditions within seconds. These complexes are structural mimics of the [Fe]-hydrogenase active site and like the natural enzyme, a labile ligand at the sixth coordination site is essential to the catalytic activity.

Full text of DOI:10.1002/ejic.201801012

A Journal of
Accepted Article
Title: Ruthenacyclic carbamoyl complexes: Highly efficient catalysts for
organosilane hydrolysis
Authors: Chandan kr Barik, Rakesh Ganguly, Yongxin Li, and Weng
Kee Leong
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
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the VoR from the journal website shown below when it is published
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To be cited as: Eur. J. Inorg. Chem. 10.1002/ejic.201801012
Link to VoR: http://dx.doi.org/10.1002/ejic.201801012

European Journal of Inorganic Chemistry
10.1002/ejic.201801012
Ruthenacyclic carbamoyl complexes: Highly efficient
catalysts for organosilane hydrolysis
Chandan Kr Barik, Rakesh Ganguly, Yongxin Li, and Weng Kee Leong*
Division of Chemistry & Biological Chemistry, Nanyang Technological University, 21 Nanyang Link,
Singapore, 637371. *E-mail: chmlwk@ntu.edu.sg.
ABSTRACT: The ruthenacyclic carbamoyl complexes [RuX(2-NHC(O)C
5
H
3
NR)(CO) (NCMe)] (R =
2
H and Me; X = Br and SC -o,o-Me ) are excellent catalysts for the hydrolysis of organosilanes, partic-
6
H
3
2
ularly towards primary silanes, generating hydrogen under ambient conditions within seconds. These
complexes are structural mimics of the [Fe]-hydrogenase active site and like the natural enzyme, a labile
ligand at the sixth coordination site is essential to the catalytic activity.
INTRODUCTION
Realization of the “hydrogen economy” as an alternative energy source to fossil fuels is contingent upon
1
-4
5
the solution of a number of challenges. One of these is a cheap and efficient means of production, for
6
-9
which the hydrogenases, which are capable of generating hydrogen from water, are of interest. Of the
three classes of hydrogenase known, viz., the [NiFe] (Type I), [FeFe] (Type II) and [Fe] (Type III) hydro-
1
0
genases, more attention has been paid to the [FeFe]-hydrogenase which is more efficient in the produc-
11,12
tion of molecular hydrogen.
The [Fe]-hydrogenase is the most recently discovered class of hydrogen-
ase, and much of the research so far has revolved around structural mimics to aid in the elucidation of the
1
3
14-17
nature of its active site, and there has been much less work on functional mimics.
1
8
A second challenge for the “hydrogen economy” is that of storage. One potential solution is to store
the hydrogen in the form of hydrides such as organosilanes, which are able to release hydrogen through
catalytic hydrolysis (Scheme 1).
1
9
cat.
Scheme 1. Silane hydrolysis.
R SiH
n
+ nH O
R4-n
+ nH2
Si(OH)n
4
-n
2
The only by-products are organosilanols, which are themselves valuable building blocks for the polymer
and materials industry, and in various organic transformations.2 The use of primary silanes is desirable
as it can give up to three equivalents of hydrogen. Although a large number of catalysts for the hydrolysis
0,21
2
2
20,23,24
25,26
27,28
29,30
31
of organosilanes, based on iron, ruthenium,
rhodium,
iridium,
rhenium,
palladium,
silver,3 gold and zinc, have been investigated, these have mainly been with secondary and tertiary
2,33
34
35
silanes. The hydrolysis of primary silanes have only been reported for heterogeneous catalysts based on
3
6
37
38
39,40
41
42
cobalt, copper, silver, gold,
and platinum, and one homogeneous catalyst based on rhenium.
We have recently embarked on a program to synthesise ruthenium-based structural analogues of the
4
3,44
[
Fe]-hydrogenase active site, such as the ruthenacyclic carbamoyl complexes 1 (Figure 1b).
These
complexes share a similarity with the natural [Fe]-hydrogenase in that the ligand at the sixth coordination
site (acetonitrile) is labile; in the [Fe]-hydrogenase, this was thought to be responsible for the activation
of dihydrogen. We therefore hypothesized that such complexes may be active catalysts. In the process,
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European Journal of Inorganic Chemistry
10.1002/ejic.201801012
we have discovered that they are indeed efficient catalysts for the hydrolysis of organosilanes and, in
particular, primary silanes. This study is reported here.
(a)
(b)
HN
N
R
N
OH
CO
CO
O
Ru
O
Fe
CO
X
NCMe
unknown
CO
S
ligand
1
Cys
a
X = Br; R = H
Me b
(
), ( )
X = o,o-Me -C H R = Me
S;
( )
c
2
6
3
Figure 1. Structure of (a) the active site of [Fe]-hydrogenase, and (b) the ruthenacyclic carbamoyl com-
plexes 1.
RESULT AND DISCUSSION
The complexes 1 catalyse the hydrolysis of a wide range of organosilanes (Table 1).
Table 1. Hydrolysis of various organosilanes catalyzed by 1.
Ph
Si
H
Ph
Si
1
mol %)
3
(
+
3 H-H
+
3 H OH
H
H
CH CN
3
HO
OH
OH
Silane
1a
yield
(%)
1b
yield
(%)
Time
H
2
Silanol
yield (%)
97
Time
(min)
H
2
Silanol
yield (%)
97
a
a
(min)
PhSiH
(CH
Ph SiH
CH CH
CH
PhMe
Et SiH
SiH
3
20 sec
5
93
96
97
95
94
97
96
<1
<1
64
20 sec
5
92
97
96
94
92
94
95
<1
<1
60
CH
3
2
)
5
SiH
3
95
94
2
2
20
94
20
93
Ph(CH
2
2
2
)
2
SiH
2
25
92
25
90
(
o-ClC
6
H
4
2
2
) SiH
2
25
92
25
88
2
SiH
30
90
30
90
3
40
92
40
90
Ph
3
120
120
120
<1
120
120
120
<1
(iPr)
SiH
<1
<1
3
PMHSb
54
50
All reactions were carried out with silane (0.4 mmol), H
2
O (4 mmol) and catalyst (3 mol%) in acetonitrile
o
at 25 C. Complex 1c showed similar catalytic activity to 1a and 1b for the hydrolysis of PhSiH , and was
3
a
not studied further. Yields are with respect to amount of organosilane used, with anisole as internal stand-
b
ard. PMHS = Poly(methylhydrosiloxane).
The reaction of phenylsilane with water in the presence of 1a, for example, gives an immediate and
profuse effervescence of hydrogen gas even at room temperature. The reaction proceeds significantly
faster in the presence of excess water, but no gas evolution is observed in the absence of 1a or under
anhydrous conditions. A number of different solvents may be used, including acetonitrile, acetone and
tetrahydrofuran. The efficiency of 1a is similar in these solvents, with organosilanol as the only by-prod-
2
2,40
uct. The secondary and tertiary organosilanols are stable at room temperature,
but the primary orga-
nosilanols convert slowly to siloxane in these solvents.3 This is consistent with the earlier report that
6,42
2
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European Journal of Inorganic Chemistry
10.1002/ejic.201801012
tertiary organosilanes are stable in tetrahydrofuran but slowly converted to siloxane in a low dielectric
2
2
constant solvent such as chloroform. An optimization study with phenylsilane shows that the optimal
catalyst loading of 1a is 3 mol% (Table S1). That 1a shows significant selectivity for primary silanes
(
RSiH
silanes (R
above, although several metal-based catalysts have been reported for organosilane hydrolysis,
of them displayed such fast rates; this is the first example in which hydrolysis is completed within a few
3
) is particularly interesting; the rates are much faster than for the secondary (R
2
SiH ) and tertiary
2
2
2
3
SiH), and is probably related to the steric bulk of the organosilane molecule. As mentioned
2
2-42
none
-1
38-40
seconds, with a TOF estimated at ~6000 h (Table S2).
Recyclability of the catalyst has been tested
for up to five cycles; the yields show an initially slow but steady decline and falls to 68% by the fifth
cycle (Figure S1). This is a higher catalyst stability than the iron analogue [Fe(2-
22
NHC(O)C
5
H
4
N)(CO)(MeCN)
3
6
][PF ].
Substitution of the MeCN ligand in 1 with a phosphine (PMe
3
) gives the phosphine-substituted deriva-
tives 2, which have been characterized spectroscopically and their structures have been confirmed by x-
ray crystallography (see ESI). These are, however, catalytically inactive and suggest that lability of the
1
MeCN ligand is important for catalytic activity. The H NMR spectrum of a 1:1 mixture of phenylsilane
and 1b in CD
3
CN (with adventitious water) shows that while the resonance due to PhSiH
3
(δ 4.16) de-
creases slowly over time, two new resonances, a singlet at δ 4.57 and a broad singlet at δ 4.32 ppm in a
4
5
2
:1 integration ratio, begin to appear (Figure 2). The chemical shift for the latter resonance is tempera-
ture-dependent (Figure S2), and hence may be tentatively assigned to a labile hydroxyl group. It is there-
fore proposed that these two resonances are assignable to PhSiH (OH), a probable intermediate in the
2
reaction. Consistent with this is the observation that the intensities of these resonances increase initially
but then decrease and disappear completely later in the course of the reaction.
1
Figure 2. H NMR spectra of a 1:1 mixture of phenylsilane and 1b in CD
3
CN.
Given the variety of metal-catalysed hydrolysis of organosilanes which have been investigated, both
homogeneous and heterogeneous, a large variety of mechanisms have been proposed.2
3,29-31,38,41
In this
work, the only intermediate identified is PhSiH (OH). We propose a catalytic pathway which is somewhat
2
similar to that previously proposed for a ruthenium-catalysed hydrolysis of secondary and tertiary silanes;
the reaction free energies have been calculated using density functional theory (Scheme 2). Initial disso-
ciation of the CH
3
CN ligand generates the catalytically-active, 16-electron species A. Coordination of the
3
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European Journal of Inorganic Chemistry
10.1002/ejic.201801012
1
2
2
silane can be via either an end-on η or a side-on η coordination mode. Optimization of an η coordina-
1
tion mode of the silane leads to the σ-complex B, suggesting that η coordination is favoured and is con-
2
3,29
23,24
sistent with earlier reports.
An alternative pathway, involving substitution of the bromide,
is ruled
out as the thiolate derivative 1c shows similar catalytic activity to 1a and 1b.
HN
N
CO
O
Br
Ru
CO
NCMe
-MeCN
HN
N
H-H
CO
O
Ru
PhSiH3
24
Br
CO
-30
+
A
HN
N
HN
N
CO
CO
H
O
H
O
Ru
Ru
Br
Br
CO H
CO
SiH Ph
C
B
2
-45
H O
2
HN
N
PhH SiOH
2
CO
H
O
Ru
H
Br
OH
SiH Ph
CO
2
B
Scheme 2. Proposed mechanism for the catalytic hydrolysis of phenylsilane with 1b. Reaction free ener-
gies given (kJ/mol) are for solvated species in acetonitrile.
Attack of water at the silicon atom in B generates the intermediate PhSiH
2
(OH), together with a dihy-
24
drogen complex C. The dihydrogen ligand is most likely formed from a (hydridic) hydrogen atom from
2
3
the silane and a proton from water. An alternative to this step, which is a nucleophilic attack of water at
2
3,29
o
the silicon center to produce an ionic species (Scheme S1),
is endergonic (∆G = +125 kJ/mol). The
(OH) produced in
final step is the elimination of the H ligand to regenerate A. The intermediate PhSiH
2
2
this cycle should be hydrolysable through the same pathway to produce two more molecules of dihydro-
gen together with phenylsilanetriol.
The proposed mechanism resembles what has been described as an outer sphere mechanism in the con-
1
text of hydrosilylation reactions, and the η -coordinated silane in B has also been suggested in computa-
tional studies.4 Three conformations, differing in the orientation of the phenyl group of the silane, for
6,47
B have been studied computationally. The most stable conformation has the phenyl ring on the same side
…
of the pyridinyl as the Br ligand (Table 2). The Ru HSi≡ vector is significantly longer than that in the
2
2
reported ruthenium η -silane complex [[RuH
2
{(η -HSiMe
2
)
2
(C
6
H
4
)}(PCy ) ] (3)] (2.03 Å vs 1.65 Å, re-
3
2
spectively),4
8-50
whereas the H-Si bond length is significantly shorter (1.51 Å vs 1.88 Å, respectively).
4
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European Journal of Inorganic Chemistry
10.1002/ejic.201801012
The Ru∙∙∙∙Si distance is also significantly longer than that in 3 (3.31 Å vs 2.43 Å), indicating that there is
no bonding interaction between the ruthenium and silicon centers.
Table 2. Computed optimized structures and selected bond parameters of the conformers of B.
Compound
Ru-H1(Å)
2.027
Si-H1(Å)
1.514
Ru∙∙∙∙Si(Å)
3.311
Ru-H1-Si(°)
138.0
E (kJ/mol)
B
0.0
4.3
5.6
B
B
1
1.978
1.507
3.241
136.4
2
2.005
1.512
3.315
140.6
A second order perturbative analysis through a natural bond orbital (NBO) calculation on B shows that
1
the bonding interaction in the Ru-η -HSiPhH
2
unit comprises a σ-donation from the H-Si σ bond to an
antibonding Ru-C(carbamoyl) orbital, and a weaker back-donation from the Ru-C(carbamoyl) bonding
5
1
orbital to the H-Si σ* orbital (Figure 3). The Si-H bond is more polarized in B than in the free silane, as
reflected in the natural charges on the silicon and hydrogen atoms (Table S3).
Donor
Acceptor
NBO
σ
H-Si
σ*Ru-C
σ
Ru-C
σ*H-Si
Occupancy
Energy (kJ/mol)
Interaction (kJ/mol)
1.8
-1.7
0.3
1.0
1.9
-1.5
0.0
0.9
104
9
1
Figure 3. MOs involved in the Ru-η -HSiPhH
2
bonding interaction.
5
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European Journal of Inorganic Chemistry
10.1002/ejic.201801012
CONCLUSION
In this study, we have described the catalytic activity of the ruthenacyclic carbamoyl complexes
RuBr(2-NHC(O)C NR)(CO) (L)] for the hydrolysis of organosilanes. These ruthenium complexes
[
5
H
3
2
turned out to be very efficient and robust catalysts for the hydrolysis of organosilanes, with very high
TOF for primary silanes.
EXPERIMENTAL SECTION
General procedures. All experiments were performed under an argon atmosphere using standard
Schlenk techniques. Chemicals were obtained from Sigma Aldrich and were used as received. Compounds
1
were synthesized by following a previous work reported by our group.43,44 Solvents that were used for
reactions were distilled over the appropriate drying agents under argon before use. HRMS were recorded
1
13
1
in ESI mode on a Waters UPLC-Q-Tof MS mass spectrometer. H and C{ H} NMR spectra were ob-
tained on a JEOL 400 MHz spectrometer at room temperature unless stated otherwise. Chemical shifts
1
13
1
for H and C{ H} were referenced with respect to the residual resonances of the respective deuterated
solvents. Infrared spectra were recorded on a Bruker Alpha FT-IR spectrometer in a IR cell with NaCl
-1
windows and a path length of 0.1 mm at a resolution of 2 cm . Elemental analyses were performed on
PerkinElmer 2400 Series II CHN/O Elemental Analyzer in house.
General procedure for the silane hydrolysis. A sample of organosilane (0.4 mmol) was added into an
acetonitrile (2 mL) solution contatining the catalyst 1 (3 mol%) and excess H
2
O (4 mmol, 0.07 mL) at
2
5 °C. An immediate evolution of gas was observed which was collected and measured using an upward
2
2,23
delivery tube set up with an inverted measuring cylinder filled with water.
Removal of solvent af-
forded the organosilanol which was identified by comparison of the NMR spectral data with the literature
5
2
20
20
20
values: Phenylsilanetriol, Diphenylsilanediol, Dimethylphenylsilanol, Triethylsilanol. TOF for hy-
drolysis of phenylsilane was calculated with respect to the mole of phenylsilane consumed. Five consec-
utive recyclability experiments have been carried out in a same mixture of 1 (3 mol%) and water (4 mmol)
in acetonitrile (2 mL) by consecutive addition of phenylsilane (0.4 mmol).
General procedure for the preparation of 2. In a typical reaction, PMe (0.05 mmol) was added into
3
a solution of 1 (0.05 mmol) in acetonitrile (5 mL). The resulting mixture was then stirred for 30 min at
ambient temperature. Slow evaporation of the solvent at room temperature afforded 2 as white crystals
after 2 d (see ESI).
Crystallographic studies. Diffraction-quality crystals were grown from acetonitrile (2) mounted on
quartz fibers. X-ray diffraction data were collected at 103(2) K on a Bruker X8 APEX system, using Mo
5
3
Kα radiation, with the SMART suite of programs. Data processing and correction were made for Lorentz
5
4
55
and polarization effects with SAINT, and for adsorption effects with SADABS. Structural solution
5
6
and refinement were carried out with the SHELXTL suite of programs. The structures were solved by
direct methods to locate the heavy atoms, followed by successive difference maps for the light, non-
hydrogen atoms. Appropriate restraints were placed on all disordered parts. All non-hydrogen atoms were
refined with anisotropic displacement parameters in the final model. All the organic hydrogen atoms were
placed in calculated positions and refined with a riding model. The crystallographic data are summarized
in Table S5.
Computational studies. The computational studies were carried out using density function theory
5
7
58
(
DFT), utilizing the hybrid functional of Truhlar and Zhao (M06). The basis set used was def2TZVP,
for the transition metals, and 6-311+G(2d,p) for the light atoms. The polarized continuum model (PCM)
was employed to describe the solvated species. Spin-restricted calculations were used for structural opti-
mization, harmonic frequency calculations and to evaluate zero-point energy (ZPE) corrections. Opti-
mized geometries were characterized as equilibrium structures with all real frequencies. All calculations
were performed using the Gaussian 09 suite of programs.59
6
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European Journal of Inorganic Chemistry
10.1002/ejic.201801012
ASSOCIATED CONTENT
Supporting Information
CCDC 1820444 (2b), 1820445 (2a) and 1852148 (2c) contain the supplementary crystallographic data
for the structures reported. These are available from the Cambridge Crystallographic Data Centre. Opti-
mization of the catalytic reaction, crystallographic tables, and optimized geometry of computed structures.
This material is available free of charge via the Internet at http:// pubs.acs.org.
AUTHOR INFORMATION
*
E-mail: chmlwk@ntu.edu.sg
ACKNOWLEDGEMENTS
This work was supported by grants from the Nanyang Technological University and the Ministry of Ed-
ucation (research grant no. M4011793), and from the Agency for Science, Technology and Research
(
A*STAR, SERC grant no. 1521200076). C.K.B is grateful to the university for a Research Scholarship.
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European Journal of Inorganic Chemistry
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For Table of Contents Only
Graphic
H O
H-H
2
R
n
SiH4-n
HN
N
R
CO
O
SiR
n
Ru
H
X
CO
OH
n
R SiH
4-n
H
6 3 2
R = H, Me; X = Br, SC H -o,o-Me
Synopsis
The ruthenacyclic carbamoyl complexes [RuX(2-NHC(O)C
5
H
3
NR)(CO)
2
(NCMe)] (R = H and Me; X =
Br and SC -o,o-Me ) are excellent catalysts for the hydrolysis of organosilanes, particularly towards
6
H
3
2
primary silanes, generating hydrogen under ambient conditions within seconds. These complexes are
structural mimics of the [Fe]-hydrogenase cofactor; a labile ligand at the sixth coordination site is essential
to the catalytic activity.
1
0
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