Hydrogenation and Hydrosilylation of Nitrous Oxide Homogeneously Catalyzed by a Metal Complex

Article abstract of DOI:10.1021/jacs.7b02124

Due to its significant contribution to stratospheric ozone depletion and its potent greenhouse effect, nitrous oxide has stimulated much research interest regarding its reactivity modes and its transformations, which can lead to its abatement. We report the homogeneously catalyzed reaction of nitrous oxide (N₂O) with H₂. The reaction is catalyzed by a PNP pincer ruthenium complex, generating efficiently only dinitrogen and water, under mild conditions, thus providing a green, mild methodology for removal of nitrous oxide. The reaction proceeds through a sequence of dihydrogen activation, "O"-atom transfer, and dehydration, in which metal-ligand cooperation plays a central role. This approach was further developed to catalytic O-transfer from N₂O to Si-H bonds.

Full text of DOI:10.1021/jacs.7b02124

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Communication
Hydrogenation and Hydrosilylation of Nitrous Oxide
Homogeneously Catalyzed by a Metal Complex
Rong Zeng, Moran Feller, Yehoshoa Ben-David, and David Milstein
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.7b02124 • Publication Date (Web): 06 Apr 2017
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Hydrogenation and Hydrosilylation of Nitrous Oxide Homogeneous-
ly Catalyzed by a Metal Complex
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Rong Zeng, Moran Feller, Yehoshoa Ben-David, David Milstein*
Department of Organic Chemistry, Weizmann Institute of Science, Rehovot, 76100, Israel
Supporting Information Placeholder
ABSTRACT: Due to its significant contribution to strato-
spheric ozone depletion and its potent greenhouse effect,
nitrous oxide has stimulated much research interest regard-
ing its reactivity modes and its transformations, which can
lead to its abatement. We report the homogeneously cata-
lyzed reaction of nitrous oxide (N2O) with H2 to yield water
and N2. The reaction is catalyzed by a PNP pincer ruthenium
complex, generating efficiently only dinitrogen and water,
under mild conditions, thus providing a green, mild method-
ology for removal of nitrous oxide. The reaction proceeds
through a sequence of dihydrogen activation, “O”-atom
transfer, and dehydration, in which metal-ligand cooperation
(MLC) plays a central role. This approach was further devel-
oped to catalytic O-transfer from N2O to Si–H bonds.
dihydroxoruthenium complex
(DMPE)2Ru(OH)2 was
formed, preventing water formation and thus prohibiting
catalytic hydrogenation.7 In 2007, Caulton reported that the
reaction of (PNP)Os(H)3 (2) (PNP = N(SiMe2CH2PtBu2)2) with
one atmosphere of N2O resulted in formation of H2O and
(PNP)OsH(N2). A separate reaction of the later with hydro-
gen slowly formed the complex (PNP)Os(H)3 (2).6c No cataly-
sis was reported. In 2015, Piers reported a formal stochio-
metric hydrogenation of N2O using a PCsp2P iridium pincer
carbene complex 3,6d which reacts with N2O with loss of N2
to form an iridiaepoxide complex; reaction of the latter with
H2 followed by heating resulted in release of H2O. However,
no catalytic turnover was observed. In 2016, Grützmacher
reported the Rh-catalyzed dehydrogenative coupling of alco-
hols using N2O as a hydrogen acceptor, which proceeds by
metal-ligand cooperation.6e Mechanistic studies of this sys-
tem showed that reaction of N2O with H2 in the presence of
complex 4 generated N2, and catalysis was mentioned, but
catalytic data (TON, conversion, or yield) was not reported.
To the best of our knowledge, there is currently no detailed
report on homogeneously catalyzed hydrogenation of nitrous
oxide.
Nitrous oxide (N2O), emitted due to agriculture activities,
industrial processes, combustion of fossil fuels and biomass,
is a potent greenhouse gas and regulator of atmospheric
ozone concentrations.1,2 While accounting for only 6% of all
greenhouse gas emissions from human activities, nitrous
oxide shows ca. 300 times greater warming potential than
CO2.3 Due to its highly destructive environmental effects, the
degradation, reduction, and/or application of nitrous oxide
have drawn much attention.4 Hydrogenation of nitrous oxide
using dihydrogen, which is driven by release of dinitrogen
and water, is considered an attractive reductive process.
While there are reports on catalytic hydrogenation reactions
of N2O by heterogeneous systems, (metal surfaces, zeolites),5
homogeneously catalyzed reactions by metal complexes are
highly desirable, as they may be more amenable to catalytic
design by catalyst structural modifications, and might occur
under mild, selective conditions. Such systems may also shed
light on mechanistic steps of importance regarding N2O acti-
vation.
Stochiometric hydrogenation of N2O involving metal com-
plexes was reported (Scheme 1).6 In seminal work by Berg-
man in 1998,6b the reaction of (DMPE)2Ru(H)2 1 (DMPE = 1,2-
bis(dimethylphosphino)ethane) with one equiv of N2O af-
forded the hydroxoruthenium complex (DMPE)2Ru(H)(OH),
which further reacted with hydrogen gas to regenerate com-
plex 1 and release a water molecule, representing stepwise
stoichiometric hydrogenation of N2O. Using excess N2O, the
Scheme 1: Homogeneous hydrogenation of N2O
To enable homogeneously catalyzed hydrogenation of ni-
trous oxide, several challenges have to be met: firstly, high
selectivity in the sequential reaction of N2O and H2 in the
catalytic cycle is required, since nitrous oxide and dihydro-
gen are in large excess relative to the catalyst. In addition,
over-reduction by hydrogen or over-oxidation by nitrous
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oxide can inhibit the catalytic efficiency of the reaction.
Thirdly, the catalyst should be active in the presence of ex-
cess amount of the generated water.
sulted in a lower TON (10 TONs / 36 h, <1% conversion of
N2O), complex 5 (P = P(iPr)2) achieved the best result, name-
ly 2.2 mmol of water (220 TONs, 17% conversion for N2O)
were formed in 36 h. Significantly, the NMR spectra of the
reaction solution showed that most of the starting ruthenium
complex was converted to the complex (PNP)RuH(CO)(OH)
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5
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8
Here we report the development of the homogeneously
catalyzed hydrogenation of N2O with H2. The reaction is
catalyzed by ruthenium pincer complexes and it very likely
involves a unique mechanism based on metal-ligand cooper-
ation (MLC). The reaction proceeds smoothly in high TON
(TON = turnover number) under very mild conditions, thus
providing a highly efficient method for hydrogenation of
nitrous oxide. Moreover, the reaction was extended to cata-
lytic O-transfer from N2O into Si−H bonds.
1
14 (spectrum iv in Figure 1; H NMR for Ru–H bond: δ -14.7
(t, 2JPH = 18.0 Hz); 31P{1H} NMR, δ = 74.0 (s); ESI analysis: MS-
ESI for C20H36NOP2Ru (MW = 470, (M-OH)+; for full mass
data, see SI). Complex 14 was independently synthesized
from 5 and H2O (spectrum v in Figure 1). Moreover, the cor-
responding reaction using 14 as catalyst led to an even better
result (307 TONs /37 h, 24% conversion for N2O), indicating
that complex 14 is very likely involved in the catalytic cycle,
and is the resting state of the catalytic cycle. Replacing the
CO ligand by N2 decreased the yield significantly (110 TON
for 10 vs 61 TON for 1112d). The acridine-based PNP rutheni-
um complex 1312e was less efficient than complex 5, affording
94 TON (7% conversion for N2O) in 36 h.
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In recent years, our group has developed a series of transi-
tion metal complexes with pyridine- and acridine-based
LNL -type (L = N or P) pincer ligands, capable of facile acti-
vation of various X−H bonds, including H−H, O−H, N−H,
C−H, B−H, and S−H bonds via metal-ligand cooperation.8 As
a typical example, the pyridine-based PNN-ruthenium com-
plex 6, first reported by us in 2005,9 can undergo a reversible
hydrogenation/dehydrogenation sequence via metal-ligand
cooperation (MLC) (Scheme 2).9 Similarly, O–H bond activa-
tion of H2O with dearomatized complex 6 takes place
smoothly and reversibly at room temperature.10 Both reac-
tions proceed with no change in the formal metal oxidation
state. These two reversible reactions, and the stability of the
complex under excess of water, encouraged us to explore the
catalytic hydrogenation of nitrous oxide by pyridine-based
pincer Ru complexes, based on metal-ligand cooperation.
Table 1: Catalyst Screening for Hydrogenation of N2Oa-c
Scheme 2: Reversible activation of H2 and H2O by 6.
Initially, the hydrogenation of N2O was examined using
0.01 mmol of the PNN-ruthenium complex 6 (0.08 mol%
catalyst) and ca. 13 mmol of N2O11 and 50 psi of H2 in a 90 mL
of Fisher-Porter tube (50 psi of H2 is respondent to 13 mmol
o
at rt). After heating in 5 ml THF at 65 C for 36 h, 0.13 mmol
1
of H2O was detected by H NMR of the reaction mixture us-
a
All the reactions were conducted in a 90 mL Fisher-
ing mesitylene as internal standard with calibration. A con-
trol experiment without the catalyst failed to afford products.
Thus, the homogeneously catalyzed reaction (13 TON, 1%
conversion for N2O) has been realized. The relatively-low
turnover number is probably due to decomposition of the
catalyst since the free PNN ligand and the corresponding
phosphine oxide were observed by 31P{1H} NMR of the reac-
tion mixture. Various pyridine-based dearomatized rutheni-
um pincer complexes were then examined (Table 1). Replac-
ing the diethylaminomethylene group (Et2NCH2-) of the pin-
cer ligand by a 2-pyridinyl group resulted in a significant
yield increase. Thus, using the PN(Py) complexes 8 (P =
P(tBu)2)12a and 9 (P = P(iPr)2) resulted in an increase in the
TONs to 53 (4% conversion for N2O) and 28 (2% conversion
for N2O), respectively. However, complete decomposition of
the catalysts was observed by 31P{1H} NMR spectroscopy.
Compared to the PNN or PN(Py) complexes, the PNP ruthe-
nium complex 10 (P = P(tBu)2)12b exhibited higher stability
and led to a higher TON (110 TONs / 37 h, 8% conversion for
N2O). The phosphine group of the PNP ligands were then
modified; while use of the PNP complex 12 (P = PPh2)12c re-
b
Porter tube using 13 mmol of H2 and N2O in 5 mL THF. All
the complexes except 13 were freshly prepared from the cor-
responding aromatized (pincer)RuH(Cl)(L) with one equiva-
t
lent of BuOK in THF and used directly in the reactions.
c
Complex 13 was obtained similarly using KHMDS as base.
The TONs are based on the generated H2O as measured by
1H NMR of the reaction mixture using mesitylene as internal
standard (see SI for details).
To have a better understanding of this catalytic transfor-
mation and to further develop it, the reaction mechanism
was explored by studying individual steps that might be in-
volved in the catalytic cycle (Scheme 3, Table S1 (see SI),
and Figure 1). Firstly, the reaction of the dearomatized ru-
thenium complex 5 (spectrum i in Figure 1) with dihydrogen
is known to occur smoothly to afford the ruthenium trans-
dihydride complex 15 (spectrum ii in Figure 1, pathway a in
Scheme 3).13 On the other hand, in the absence of H2, N2O
was found to decompose complex 5, resulting in a complicat-
ed mixture (pathway e), which failed to convert to the ruthe-
nium hydroxo complex 14 in the presence of excess H2
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(pathway f). Importantly, the competitive experiment of 5 in
tion of ruthenium hydroxide 14 with H2, combining water
release and hydrogen addition via metal-ligand cooperation
(pathway d).
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the presence of both N2O and H2 (1:1 mixture) resulted in
formation of the ruthenium trans-dihydride complex 15 as
the only product. Thus, the much faster reaction of 5 with H2
than with N2O inhibits the decomposition of 5 and enables
the whole catalytic cycle. Since the hydrogenation of 5 is a
reversible reaction, via metal-ligand cooperation (pathway
b), catalyst 5 can be regenerated from 15, as observed under
vacuum or upon heating.13
Complex 15 was found to be the best catalyst in the hydro-
genation of N2O. Full conversion of nitrous oxide and the
highest TON were achieved by generating it in situ from
complex 15 (0.03 mmol, 0.23% of catalyst) and increasing the
reaction time to 48 h (eq. 1). The produced 83% yield of dini-
trogen (360 TON based on N2) was determined carefully by
GC, and 96% yield of H2O (417 TON based on H2O) was
measured by 1H NMR with calibration.11
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Based on these results, we propose that the mechanism of
hydrogenation of nitrous oxide follows the reaction sequence
of pathway a-c-h, involving hydrogenation of the dearoma-
tized PNP pincer complex 5 by metal-ligand cooperation
(MLC) to afford the ruthenium trans-dihydride compound
15, followed by (likely rate determining) selective mono oxy-
gen transfer from nitrous oxide to give complex 14, and water
release by MLC to regenerate complex 5, thus completing an
efficient, selective catalytic cycle. Essentially, each one of the
complexes 5, 14 and 15, which are involved in the catalytic
cycle, can serve as a catalyst, as we indeed observed. Howev-
er, due to the potential decomposition of 5 if N2O is added
prior to H2, complex 15 is practically the best catalyst. To be
mentioned, due to the reversible hydration/dehydration se-
quence via metal-ligand cooperation, it is difficult to isolate
complex 14 and it was characterized in situ.
Scheme 3: Mechanistic studies of individual steps
Silicon-oxygen bond formation of silane with nitrous oxide
is the key process for deposition of non-stoichiometric sili-
con oxide or semi-insulating polysilicon (SIPOS), which is
used as a substitute for silicon dioxide as passivation material
in high voltage power devices.15 Thus, homogeneous “O”-
atom transfer of nitrous oxide into silane was then examined
by using catalyst 5 under N2O atmosphere (50 psi) (Table 2):
the reaction of PhMe2SiH 16a with nitrous oxide took place
smoothly using 1 mol% of catalyst, affording the desired si-
lanol 17a together with disilyl ether 18a in 32% and 64%
yields, respectively. H2 was detected by GC, indicating that
the disilyl ether is formed from the direct dehydrogenative
coupling reaction of formed silanol and residual silane.
Ph2MeSiH 16b, which contains a bulkier substituent (Ph over
Me group), exhibited lower reactivity and afforded 30% of
silanol 17b together with 46% of disilyl ether 18b using 2
mol% of catalyst and increasing reaction time to 3 days. Sub-
strate 16c with tert-butyl group afforded only silanol 17c in
46% yield together with 54% of recovered starting material.
No disilyl ether 18c was formed because of the steric hin-
drance of the bulky substituents.
1
Figure 1: H NMR of Ru–H bonds and 31P{1H} NMR spec-
tra of complexes 5, 14, and 15 in THF and the correspond-
ing reactions
Moreover, even in the presence of two equiv of N2O, only
mono “O”-atom transfer took place upon reaction with 15,
quantitatively forming the hydrido hydroxo complex 14
(spectrum iii in Figure 1, pathway c in Scheme 3).14 This is
important, since double insertion to give the dihydroxo
complex (as observed by Bergman6a-b) would hinder subse-
quent water elimination. Reversible water elimination from
complex 14 is facilitated by the trans effect of Ru–H bond,
affording the dearomatized PNP pincer catalyst 5 under vac-
uum (pathway h). Furthermore, the ruthenium trans-
dihydride complex 15 was regenerated directly by the reac-
In summary, the homogeneously catalyzed hydrogenation
of nitrous oxide by a metal complex has been developed.
High efficiency and high TON are achieved using the PNP
pincer ruthenium complex 15 as the catalyst. Studies of stoi-
chiometric steps indicate that the reaction involves
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(5) For selected reports on heterogeneous hydrogenation of ni-
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a The reactions were conducted using a THF solution con-
taining 0.01 mmol of catalyst 5 and 1.0 mmol (for PhMe2SiH)
t
or 0.5 mmol (for Ph2MeSiH and BuMe2SiH) of substrate un-
b
der 50 psi of N2O. The yields (based on the silane) were
determined by GC using standard curve due to the low boil-
c
ing point of the product. 54% of the starting material was
recovered.
Metal-Ligand Cooperation (MLC). Thus, H2 addition to the
dearomatized catalyst 5 takes place with aromatization to
form complex 15, followed by mono-oxygen transfer from
N2O to a Ru–H bond, and subsequent water release by MLC,
regenerating the dearomatized complex. Moreover, catalytic
“O”-atom transfer from nitrous oxide to Si–H bonds of
silanes, catalyzed by the dearomatized 5, was also demon-
strated. Further studies in this area are being carried out in
our laboratory.
ASSOCIATED CONTENT
Supporting Information
Experimental procedures; spectral data. This material is
available free of charge via the Internet at
http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
(11) For details regarding calibration of the amount of N2O consid-
ering its solubility in THF, see SI.
david.milstein@weizmann.ac.il
(12) a) Balaraman, E.; Gnanaprakasam, B.; Shimon, L. J.; Milstein,
D. J. Am. Chem. Soc. 2010, 132, 16756; b) Khaskin, E.; Iron, M. A.;
Shimon, L. J. W.; Zhang, J.; Milstein, D. J. Am. Chem. Soc. 2010, 132,
8542; c) Jia, G.; Lee, H. M.; Williams, I. D. Organometallics 1997, 16,
3941; d) Zhang, J.; Gandelman, M.; Shimon, L. J. W.; Rozenberg, H.;
Milstein, D. Organometallics 2004, 23, 4026; e) Gunanathan, C.;
Milstein, D. Angew. Chem. Int. Ed. 2008, 47, 8661.
Notes
The authors declare no competing financial interests.
ACKNOWLEDGMENT
This research was supported by the European Research
Council (ERC AdG 692775). D.M. holds the Israel Matz Prof-
essorial Chair of Organic Chemistry. R.Z. thanks the Faculty
of Chemistry for being awarded a Dean’s Fellowship.
(13) Zhang, J.; Leitus, G.; Ben-David, Y.; Milstein, D. Angew. Chem.
Int. Ed. 2006, 45, 1113.
(14) For “O”-atom transfer into M–H bond of N2O to form M–OH,
see: M = Ru: refs. 6a-6b, 7, and 10; for M = Rh, see ref. 6e; for M = Hf,
see: a) Vaughan, G. A.; Rupert, P. B.; Hillhouse, G. L. J. Am. Chem.
Soc. 1987, 109, 5538.
(15) Fayolle, F.; Couderc, J.-P.; Duverneuil, P. Chem. Vap. Deposi-
tion 1996, 2, 255, and the references therein.
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ACS Paragon Plus Environment