Hydrogenation of Carbon Dioxide to

Methanol using a Homogeneous

Ruthenium–Triphos Catalyst:
From Mechanistic Investigations
to Multiphase Catalysis

Kelompok 5
Adawiah
Purnomo Arif Abdillah
Fadhnul Ashim
 INTRODUCTION
CO2 sebagai alternatif sumber Karbon Konversi CO2  Metanol
 Ketersediaan sumber karbon dan konsumsi  Produksi metanol pada skala
energi secara global yang tidak seimbang megaton/tahun
 Mudah tersedia, Dihasilkan dalam skala besar  Metanol sebagai bahan bakar alternatif
 Tidak beracun  Bahan dasar pada pembuatan bahan kimia

Timinaga et al., Cakhraborty et al., Leitner et al., 2015

1995
 Hidrogenasi CO2  Metanol
 Single site catalyst Ru(CO)12,
Alkali Iodide (240 °C, 80 bar)
 Produk berupa metanol,
metana dan CO
2010 (This report)
 High energy reduction agent  Direct pathway
(Boranes) dan H2  Single molecullar
 Indirect route via the conversion of catalyst Ru-Triphos
CO2-derived intermediates  Tanpa penambahan
(organic carbonate, carbamat dan alkohol
formate ester)
 Previously shown by Milstein et al.,
2011; Sanford/Huff, 2011;
klankemeyr/Leitner, 2012
Hydrogenation pathway of CO2  Metanol

Reported by Milstein et al., 2011;

Sanford/Huff, 2011; klankemeyer/Leitner,
2012 (Upper pathway)
Reported by Leitner et al., 2015
(Lower pathway)
RESULT AND DISCUSSION
01 Basic reactivity and identification of the active
species

02 Mechanistic pathways on the basis of DFT

calculations
 Formation of hydroxymetalonate via formic acid
 Cleavage of the C-O bond and generation of
formaldehyde
 Hydrogenation of formaldehyde to methanol

03 Parameter variation and catalyst recycling in a

biphasic system
 RESULT AND DISCUSSION

Scope Pembahasan NMR experiment analysis

Precursor catalyst  a sharp signal at 3.27 ppm in the 1H-NMR spectr

um indicated the catalytic formation of MeOH in t
he absence of any alcohol additive with a TON (tu
rnover number = mmol MeOH per mmol catalyst
of 35.

 Thus, one of the species formed must have been

able to serve as a catalyst for the hydrogenation
Catalitically of CO2 to methanol.
active
Intermediet

Pre-catalyst
Identification of the active species

 The cationic carbonyl complex [(Triphos)RuH(CO)2] + (5)

and in solution it was about 4% (doublet (18.6 ppm, J = 28.7
Hz) and triplet (6.3 ppm, J = 28.7 Hz) in the 31P{1H}-NMR
spectrum. The hydride signal at δ = 6.7 ppm in the [1H,31P]-
HMBC-NMR)

 dimeric complex [Ru2(µ-H)2(Triphos)2] (6), which formed in

about 2%. (sharp singlet at 43.3 ppm in the 31P{1H}-NMR
spectrum and hydride signal at 8.7 ppm in the 1H-NMR spec
trum by [1H,31P]-HMBC-NMR)

 [Ru2(Cl)3(Triphos)2]+ (7) which formed in about 6% (The

small sharp singlet at 36.7 ppm in the 31P{1H}-NMR spectru
m)

 Ruthenium–formate complexes (3a) (over 85% of the total

signal intensity in the 31P{1H}-NMR spectrum gave rise to a
broad singlet at 44.2 ppm, at 233 K resulted in the splitting
of this signal into a doublet (46.3 ppm, 2P, J = 42.5 Hz) and
a triplet (43.9 ppm, 1P, J = 42.5 Hz).
 The cationic carbonyl complex Dimeric Complex
[(Triphos)RuH(CO)2] + (5) [Ru2(µ-H)2(Triphos)2] (6)

 Signal doublet (18.6 ppm, J = 28.7 Hz) and triplet (6.3 p  The sharp singlet at 43.3 ppm in the 31P{1H}-NMR spectrum
pm, J = 28.7 Hz) in the 31P{1H}-NMR spectrum. was correlated with a broad hydride signal at 8.7 ppm in the
1H-NMR spectrum by [1H,31P]-HMBC-NMR
 The hydride signal at δ = 6.7 ppm in the [1H,31P]-HMBC
-NMR  Dimeric complex [Ru2(µ-H)2(Triphos)2] (6), which formed in
about 2%.
 (5) was synthesised in pure form by stirring complex (2)
together with 1 equivalent of HNTf2 in ethyl formate a  Using isolated 6 in the CO2 hydrogenation reaction under st
nd 60 bar H2 in the absence of CO2 for 24 hours at 14 andard conditions resulted in no formation of methanol
0 C.
 The formation of 6 as a second major deactivation pathway.
 Testing the isolated complex 5 for its catalytic activity i
n CO2 hydrogenation in the absence of alcohol (standar
d conditions: V(THF) = 2.08 mL, c(Ru) = 12 mmol/L, 1
eq. of HNTf2, p(CO2) = 20 bar at r.t, p(H2) = 60 bar at r.t
., T = 140 C, t = 24 h) only gave a TON of 4,

 Identifying the formation of 5 as a possible deactivation

pathway.

[Ru2(Cl)3(Triphos)2]+ (7)
 The small sharp singlet at 36.7 ppm in the 31P{1H}-N
MR spectrum was assigned to [Ru2(Cl)3(Triphos)2]+
(7) which formed in about 6% (according to the inte
gral ratios in the 31P{1H}-NMR spectrum).
 A CO2 hydrogenation reaction under standard conditi
ons using the [(Triphos)Ru(TMM)] (2) precursor but w
ith the addition of 1-butyl-3-methylimidazolium chlori
de (3 eq.)
 only gave a TON of 1.
 The 31P{1H}-NMR spectrum of the solution showed th
e formation of 7, 5 and [(Triphos)RuH(CO)Cl] (18) ind
icating that Ru–Triphos complexes bearing chloro li
gands are generally inactive in this transformation.
Ruthenium–formate
complexes
 The main species (over 85%) of the total signal intensity in the 31P
{1H}-NMR spectrum gave rise to a broad singlet at 44.2 ppm.
 Low-temperature NMR at 233 K resulted in the splitting of this signa
l into a doublet (46.3 ppm, 2P, J = 42.5 Hz) and a triplet (43.9 ppm,
1P, J = 42.5 Hz).
 A [1H,31P]-HMBC-NMR experiment revealed coupling of these signa
ls to a proton signal at 8.7 ppm, which is well in the range of ruthen
ium coordinated formate.
 A [1H,13C]-HMBC-NMR experiment showed the coupling of the prot
on signal at 8.7 ppm to a singlet at 178.8 ppm in the 13C-NMR corro
borating the formation of a formate-complex.
 No hydride signals corresponding to this species were detected in
the respective correlation NMR spectra.
[(Triphos)Ru(ƞ2-O2CH)(THF)]+
Identification
 The same formate complex was
generated independently by (addi
of
ng 1 eq. of HNTf2 to complex 2 in
d8-THF, followed by the addition Ru-Formate
of 1 eq. Of HCO2H at r.t.
Complex
 NMR analysis 233 K showed an
identical signals in the 31P{1H}-N
MR spectrum in about 80% of the
total intensity.

 FT-IR analysis showed a vCO stre

tching mode at 1543 cm -1, a typi
cal value for ƞ 2 -coordinated form
ate.

 Tthe structure of this complex as

[(Triphos)Ru(ƞ2-O2CH)(THF)]+
(3a), where the weakly bound sol
vent molecule THF accounts for
the fluxionality at room temperatu
re (Scheme 3).
 Supporting Data of Identification [(Triphos)Ru(ƞ2-O2CH)(THF)]+

 The formation of a non-fluxional formate complex (3B) (shceme 4) with signal spectrum (d, 42.8 ppm, 2P; t, 29.6 ppm, 1P, J = 42.2 Hz).

 FT-IR analysis showed a vCO stretching mode at 1544 cm -1, consistent with the structure [(Triphos)Ru(ƞ2-O2CH)(MeCN)]+ (3b).

 Decreasing of the signals of 3b over a period of 5 hours at room temperature at the expense of new doublet (47.6 ppm, 2P, J = 20.6 Hz) and tri
plet (5.5 ppm, 1P, J = 20.6 Hz) signals. In parallel, the formate signal at 8.7 ppm disappeared, formation of an upfield hydride signal (dt, 5.5 pp
m, J = 105.0 Hz, J = 19.3 Hz) in the 1H-NMR spectrum.

 These NMR-data are consistent with the decarboxylation of 3b to give the complex [(Triphos)Ru(H)(MeCN)2]+ (8) (Scheme 4).

 Consequently, the formation of the formate complex 3 from 2 in the presence of HNTf2 under CO2 and H2 pressure is most plausibly explained
via reversible CO2-insertion into the analogous solvent-coordinated cationic Ru–hydride complex as an intermediate.

 Ruthenium–formate complexes are well known as intermediates in the CO2 hydrogenation to formic acid.
 a solution of 3a was prepared from 2/HNTf2 (1:1) and HCO2H in d8-THF, p(H2), and T = 140 °C in an external oil bath in a high-
pressure NMR tube for 40 minutes (Scheme 5).
Identification
 Tthe 31P-NMR spectra showed the formation of [Ru2(µ-H)2(Triphos)2] (6) in around 44% yield.

 Furthermore, in situ high pressure NMR studies using complex 2 directly under turnover conditions (2/HNTf2 (1:1), d8-THF, T =
of
80 °C, p(H2) = 60 bar, p(CO2) = 20 bar) revealed that complex 3a was formed immediately after pressurisation and remained th
e major detectable phosphorus containing species present in solution throughout the reaction. Ru-Formate
 No hydride signals that could be related to an active species were observed in the 1H-NMR spectra. Complex as
 These data indicate that the cationic hydride intermediate is converted to the formate complex [(Triphos)Ru(ƞ2-O2CH)(THF)]+ Kinetically
(3a).
competent
 In order to probe this assumption, we decided to start from an isolated cationic complex precursor with the analogous cationic a
cetate complex. Stirring [(Triphos)Ru(ƞ2-OAc)Cl] (9) + 1 eq. of AgNTf2 for 3 h at 60 °C in THF led to the precipitation of AgCl. intermediet
 The 31P{1H}-NMR spectrum showed only one sharp singlet at 44.0 ppm.

 After filtration of the yellow solution over silica and removal of the solvent in vacuo a yellow powder was obtained. Characterisat
ion of the material by 1H-, 13C- and 19F-NMR, FT-IR and ESIHRMS revealed the presence of the cationic [(Triphos)Ru(ƞ2-OAc)]
+ fragment (see ESI†).
 Crystallisation from DCM layered with pentane gave yellow single crystals of complex 4a where the open coordinati
on site was saturated with H2O from adventitious traces of water (Fig. 2).

 Thus, the acetate complex in solution can be formulated as [(Triphos)Ru(ƞ2-OAc)(S)][NTf2] (4) with S being a free c
oordination site or weakly bound solvent molecule.

 The formation of dimeric or trimeric species [(Triphos)Ru(µ-OAc)]x[NTf2]x could be excluded by using two structurall
y different Triphos derivatives and stirring an equimolar (12.5 mmol) mixture of [(Triphos)Ru(ƞ2-OAc)Cl] (9) and [(Tr
iphos-anisyl)Ru(ƞ2-OAc)Cl] (10) (Triphos-anisyl = 1,1,1-tris{bis(4-methoxyphenyl)phosphinemethyl}ethan) together
with AgNTf2 (30 mmol) in toluene (1.5 mL) at 60 °C for 5 hours.

 The toluene was removed in vacuo, the residue dissolved in d2-DCM (0.5 mL), and the mixture analysed by NMR.
The 31P{1H}-NMR spectrum at room temperature showed two singlets at 43.5 and 45.3 ppm in a ratio of nearly 1:1
related to [(Triphos)Ru(ƞ2-OAc)(S)]NTf2 (4) and [(Triphos-anisyl)Ru(ƞ2-OAc)(S)]NTf2 (11), respectively.

 The absence of further signals due to mixed complexes (e.g. [Ru2(Triphos)(Triphos-anisyl)(µ-OAc)2][NTf2]2) support
s the monomeric structure of 4 in solution.

 The reactivity of the acetate complex 4 under p(CO2) =20 bar at r.t. and p(H2) = 60 bar at r.t. was investigated in a
high pressure NMR experiment (see ESI†). After 1.5 hours at 80 °C and 1 hour at 140 °C, ca. 60% (31P{1H}-NMR)
of 4 was converted to the formate complex 3a and ethanol from acetate hydrogenation was detected by 1H-NMR in
the reaction mixture.

 Methanol was indeed observed in the solution with a TON of 5, confirming that the cationic complex 4 was operati
ng as a molecularly defined direct precursor for the catalytic cycle for CO2 hydrogenation without the need of any a
cid additive.

 Identification of the formate complex 3 as the active intermediate suggests that the major role of the acid additive in
the catalytic system 2/HNTf2 is the generation of cationic species as the active site upon reductive removal of the T
MM-ligand.
Mecanistic Pathway on the basis of DFT calculation

 Hidrogenasi CO2  Metanol terjadi melalui

pembentukan formic acid dan formaldehyde.

 The intermediated are I, V, IX, XVIII,

 Starting from a cationic ruthenium-hydrid

complex (I)

 The migratory insertion CO2

 First hidrogenation (reduction of formic

acid)

 Second hidrogenation

 Third hidrogenation (hydrogenolysis of

Ru-OMe  MeOH + I
Formation of Hydroxymethanolate via formic acid (I-IX)
Cleavage of C-O bond and Generation of Formaldehyde (IX-XV)
Hydrogenation of Formaldehyde to Methanol (XV-I)
Thank you