supplementary materials for · effect of the ph on hydrogenation of nitrobenzene. section s1....

advances.sciencemag.org/cgi/content/full/4/6/eaat0761/DC1

Supplementary Materials for

Intermetallic nickel silicide nanocatalyst—A non-noble metal–based

general hydrogenation catalyst

Pavel Ryabchuk, Giovanni Agostini, Marga-Martina Pohl, Henrik Lund, Anastasiya Agapova,

Henrik Junge, Kathrin Junge, Matthias Beller

Published 8 June 2018, Sci. Adv. 4, eaat0761 (2018)

DOI: 10.1126/sciadv.aat0761

This PDF file includes:

section S1. Materials and methods

section S2. Procedure for the catalyst preparation (fig. S1).

section S3. TEM and EDX data (fig. S2 to S5)

section S4. XRD diffraction patterns and data (figs. S6 to S10)

section S5. XPS spectra and data (fig. S11)

section S6. Elemental analysis of the catalysts and BET (fig. S12)

section S7. Thermogravimetric analysis (TGA; figs. S13 and S14)

section S8. Procedures for hydrogenation reactions (figs. S15 and S16)

section S9. Product characterization

section S10. Procedures for dehydrogenation reactions (figs. S17 to S19)

section S11. Catalyst recycling

section S12. Nuclear magnetic resonance (NMR) spectral charts

fig. S1. Ni-phen@SiO2-1000 after pyrolysis.

fig. S2. TEM images of the Ni-phen@SiO2-1000.

fig. S3. ABF and HAADF-STEM images of intermetallic nickel silicide catalyst

Ni-phen@SiO2-1000.

fig. S4. HAADF-STEM and EDX measurement of the intermetallic nickel silicide

catalyst Ni-phen@SiO2-1000.

fig. S5. ABF-, HAADF-STEM, and EDX measurement of the catalyst Ni@SiO2-

1000 prepared without ligand.

fig. S6. Powder pattern of nickel-based catalysts supported on fumed silica.

fig. S7. Powder pattern of Ni-phen@SiO2-800 measured up to 148°2θ.

fig. S8. Powder pattern of various nickel-based catalysts with different ligands

(S2.3).

fig. S9. Powder pattern of various nickel-based catalysts on various supports.

fig. S10. Powder pattern of nickel catalyst on silica gel and quartz (S2.3).

fig. S11. XPS measurement of the intermetallic nickel silicide catalyst.

fig. S12. N2 adsorption-desorption isotherms and BJH desorption pore size

distribution.

fig. S13. TG-DSC-MS analysis of Ni-phen@SiO2-1000.

fig. S14. TG-DSC-MS analysis of Ni-phen@SiO2-1000.

fig. S15. Autoclave and glass vials used for hydrogenations.

fig S16. Concentration/time diagram for the hydrogenation of benzonitrile.

fig. S17. Manual burette setup.

fig. S18. Gas evolution from 1,2,3,4-tetrahydroquinaldine.

fig. S19. Gas composition analysis by GC.

table S1. Elemental analysis of the studied catalysts.

table S2. BET surface area and pore volume of the samples.

table S3. Hydrogenation of the standard substrates (Table 1 in the main text).

table S4. Hydrogenation of the nitrobenzene with SiO2-supported catalysts.

table S5. Recycling experiments.

table S6. Nickel leaching in the recycling experiments.

table S7. Effect of the pH on hydrogenation of nitrobenzene.

section S1. Materials and methods

All reactions were performed in oven (160°C) and/or flame-dried glassware under

atmosphere of dry argon unless otherwise noted. All substrates were obtained

commercially from various chemical companies: Sigma-Aldrich, TCI Europe, Alfa

Aesar, abcr GmbH and used as received. Chemicals used for the catalyst preparation:

Nickel (II) acetate tetrahydrate, 98% (Sigma-Aldrich); 1,10-phenanthroline monohydrate

(Alfa Aesar); N,N,N′,N′-Tetramethylethylenediamine, 99% (Sigma-Aldrich); Pyridine,

≥99.0% (Sigma-Aldrich); Fumed silica, AEROSIL® OX 50 (Evonik Industries); Carbon

powder, VULCAN® XC72R (Cabot Corporation Prod.); silicon carbide, -100 mesh

(Strem); Titanium(IV) oxide, Aeroxide® P25 (Sigma-Aldrich, Ar. Nr. 718467),

Aluminum oxide ɣ-phase, nanopowder, 99+% (Alfa Aesar, Ar Nr. 44757), Cerium oxide

nanopowder, <25 nm particle size (Sigma-Aldrich, Ar. Nr. 544841). Solvents: Methanol,

99% (Alfa Aesar); Etanol, 99% (Alfa Aesar); Deionized water; Ammonia solution, 7M in

methanol, (Alfa Aesar, Ar. Nr. H30382); Triethylene glycol dimethyl ether, 99% (abcr

GmbH) – distilled and stored over 4Å molecular sieves. The pyrolysis experiments were

carried out in Nytech-Qex oven. Crucibles (height – 20 mm, top Ø – 40 mm, Ar. Nr.

L219.1) and lids (Ø – 40 mm, Ar. Nr. L236.1) were purchased from Roth Industries

GmbH & Co. KG.

The TEM measurements were performed at 200kV with an aberration-corrected JEM-

ARM200F (JEOL, Corrector: CEOS). The microscope is equipped with a JED-2300

(JEOL) energy-dispersive x-ray-spectrometer (EDXS) and an Enfinum ER (GATAN)

with Dual EELS for chemical analysis. The aberration corrected STEM imaging (High-

Angle Annular Dark Field (HAADF) and Annular Bright Field (ABF)) were performed

under the following conditions. HAADF and ABF both were done with a spot size of

approximately 0.1nm, a convergence angle of 30-36°and collection semi-angles for

HAADF and ABF of 90-170mrad and 11-22mrad respectively. Dual EELS was done at a

CL of 4 cm, an illumination semi angle of 21.3 mrad and an entrance aperture semi angle

of 19.8 mrad. The solid samples were deposed without any pretreatment on a holey

carbon supported Cu-grid (mesh 300) and transferred to the microscope.

XPS data was measured by a VG ESCALAB220iXL (ThermoScientific) with

monochromatic Al Kα (1486.6 eV) radiation. Electron binding energies were corrected to

the O 1s peak of Si-O bonds at 532.9 eV. For quantitative analysis the peaks were

deconvoluted with Gaussian-Lorentzian curves, the peak area was normalized by a

sensitivity factor obtained from the element specific Scofield factor and the transmission

function of the spectrometer.

XRD powder pattern were recorded either on a Panalytical X'Pert diffractometer

equipped with a Xcelerator detector or on a Panalytical Empyrean diffractometer

equipped with a PIXcel 3D detector system both used with automatic divergence slits and

Cu kα1/α2 radiation (40 kV, 40 mA; λ= 0.015406 nm, 0.0154443 nm). Cu beta-radiation

was excluded by using nickel filter foil. Peak positions and profile were fitted with

Pseudo-Voigt function using the HighScore Plus software package (Panalytical). Phase

identification was done by using the PDF-2 database of the International Center of

Diffraction Data (ICDD).

Thermogravimetric analysis (TGA) was performed with Netzsch STA 449 F3Jupiter with

DSC-sensor. The TG-DSC-MS measurements were performed on a Sensys TG-DSC

apparatus (Setaram) coupled with a OmniStar quadrupole mass spectrometer (Pfeiffer

Vacuum).

All hydrogenation experiments were carried out in 300 mL autoclave (PARR Instrument

Company) in 8-mL glass vials, which were placed inside the autoclave.

GC Conversion and yields were determined by GC-FID, HP6890 with FID detector,

column HP530 m x 250 mm x 0.25 μm. Analysis of the gas sample in the

dehydrogenation process was performed using GC HP Plot Q (FID – hydrocarbons,

Carboxen / TCD - permanent gases), Ar - carrier gas. The GC was externally calibrated

using certified gas mixtures from commercial suppliers (Linde and Air Liquide) with the

following gas vol%:

H2: 1%, 10%, 25%, 50%, 100%

CO: 10 ppm, 100 ppm, 250 ppm, 1000 ppm, 1%, 10%

CO2: 1%, 50%

CH4: 1%

The systems allow for the determination of H2, CH4, CO and CO2 within the ranges:

H2 ≥ 0.5 vol% - 100 vol%

CO ≥ 10 ppm

CO2 ≥ 100 ppm - 100 vol%

CH4 ≥ 1 ppm

NMR data were recorded on a Bruker ARX 300 and Bruker ARX 400 spectrometers (300

or 400 MHz, 1H; 75 MHz, 13C). Spectra were referenced to residual CHCl3 (7.26 ppm 1H;

77.00 ppm 13C) or MeOD (4.870, 3.31 ppm 1H; 49.00 ppm 13C) or D2O (4.79 ppm, 1H).

Chemical shifts are reported in ppm, multiplicities are indicated by s (singlet), d

(doublet), t (triplet), q (quartet), p (pentet), h (hextet), hep (heptet), m (multiplet) and br

(broad). Coupling constants, J, are reported in Hertz. (+) and (-) representpositive and

negative intensities of signals in 13C DEPT‐135 experiments.

The Brunauer−Emmett−Teller (BET) surface areas were estimated using ASAP 2020

(Micromeritics) over a relative pressure (P/P0) range of 0−0.99. Pore size distributions

were obtained from the adsorption branch of the isotherms using the

Barrett−Joyner−Halenda (BJH) method. The sample was pretreated for 2 h under vacuum

(0.1 mbar) at 400°C.

section S2. Procedure for the catalyst preparation (fig. S1)

S2.1. Preparation of intermetallic Nickel Silicide Ni-phen@SiO2-1000 catalyst.

A 250 mL oven-dried single-necked round-bottomed flask equipped with a Allihn reflux

condenser and a Teflon-coated, egg shaped magnetic stir bar (40 × 18 mm) was charged

with Ni(OAc)2∙4H2O (373.3 mg, 1.5 mmol, 1.0 equiv.), 1,10-phenanthroline

monohydrate (594 mg, 3.0 mmol, 2.0 equiv.) and dissolved in ethanol (60 mL). After

stirring for 5 min at 25°C, the flask was immersed in an oil bath and heated at 60°C for 2

h.a To the reaction mixture 2.10 g of silica (Aerosil® OX-50) was added via a glass

funnel and the resulting heterogeneous mixture was stirred at 750 rpm for 2 h at 60°C.

The flask was taken out from the bath and cooled to ambient temperature. The solvent

was removed in vacuo (180 mbar, bath temperature 40°C, 200 rpm), then dried under oil

pump vacuum (1.0 mmHg, 23°C) for 14 h to give a light blue-green solid. The sample

was grinded to a fine powder (2.82 g) which was then transferred to a ceramic crucible

(height – 20 mm, top Ø – 40 mm) and placed in an oven. The latter was evacuated to ca.

5 mbar and then flushed with argon three times. The furnace was heated to 1000°C at a

rate of 25°C per minute and held at 1000°C for 2 h under argon atmosphere. After the

heating was switched off the oven was allowed to reach room temperature, giving the Ni-

phen@SiO2-1000 catalyst as a black powder (2.476 g). (Note: during the whole process

argon was constantly passed through the oven).

a Note: An aliquot was dissolved in acetonitrile and subjected to ESI-MS analysis, the

presence of [Ni(phen)2OAc]+ was confirmed (C26H19N4NiO2+ – 477.0).

fig. S1. Ni-phen@SiO2-1000 before (left) and after the pyrolysis (right).

S2.2. Preparation of nickel-based supported catalyst library.

The same procedure (S2.1.) has been applied for the preparation of other nickel-based

materials shown in Table 1. Ni(OAc)2∙4H2O (373.3 mg, 1.5 mmol, 1.0 equiv.), 1,10-

phenanthroline monohydrate (594 mg, 3.0 mmol, 2.0 equiv.) and dissolved in ethanol (60

mL) and supported on 2.1 g of corresponding support (Carbon, SiC, Al2O3, TiO2, CeO2)

and subsequently pyrolyzed at 600, 800 or 1000°C. Obtained materials were tested in the

hydrogenation of nitrobenzene, acetophenone and benzonitrile (table S3).

S2.3 Preparation of nickel-based catalysts. Variation of silica grade and ligand.

The procedure S2.1. has been applied for the preparation of nickel-based materials

supported on different SiO2 based materials. Ni(OAc)2∙4H2O (373.3 mg, 1.5 mmol, 1.0

equiv.), 1,10-phenanthroline monohydrate (594 mg, 3.0 mmol, 2.0 equiv.) and dissolved

in ethanol (60 mL) and supported on 2.1 g of corresponding SiO2 support (quartz,

conventional silica gel, AEROSIL® OX 50) and subsequently pyrolyzed at 1000°C.

For the ligand variation, the same procedure S2.1. has been applied. Ni(OAc)2∙4H2O

(373.3 mg, 1.5 mmol, 1.0 equiv.), nitrogen-containing ligand (TMEDA – 449 µL, 3.0

mmol, 2.0 equiv.; ammonia – 0.41 mL (25% aq. NH3), 6.0 mmol, 4.0 equiv.; pyridine –

483 µL, 6.0 mmol, 4.0 equiv.; or no ligand at all, labeled as “NL”) and dissolved in

ethanol (60 mL) and supported on 2.1 g of AEROSIL® OX 50 and subsequently

pyrolyzed at 600, 800 and 1000°C.

Obtained materials were tested in the hydrogenation of nitrobenzene (table S4).

section S3. TEM and EDX data (fig. S2 to S5)

fig. S2. ABF- and HAADF-STEM images of intermetallic nickel silicide catalyst Ni-

Phen@SiO2-1000 (a, b). The elemental maps (c-g) show the distribution of the Ni on the

SiO2 particles

a) b)

c) d) e)

f) g)

fig. S3. ABF and HAADF-STEM images of intermetallic nickel silicide catalyst Ni-

phen@SiO2-1000. Graphitic structures often not tight at the particle surface.

ABF HAADF

fig. S4. HAADF-STEM and EDX measurement of the intermetallic nickel silicide

catalyst Ni-phen@SiO2-1000.

ABF HAADF

fig. S5. ABF, HAADF-STEM, and EDX measurement of the catalyst Ni-phen@SiO2-

1000 prepared without ligand. Metallic Ni particles at SiO2 are observed. The less

HAADF contrast in the outermost areas (magnified insert) indicates a oxidic shell. An

analysis by EDXS for this area was not possible due to the particles position at silica.

Silicon to oxygen ratio for both EDX measurements is nearly constant, indicating that the

particle consists of metallic Ni. Overall, particle size ranges from 10 to 50nm.

1

2

0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00

keV

018

0

100

200

300

400

500

600

700

800

900

1000

Coun

ts

CKa

NK

aO

Ka

SiK

a

NiL

lN

iLa

NiK

esc

NiK

a

NiK

b

CuLl

CuLa

CuK

a

CuK

b

0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00

keV

017

0

100

200

300

400

500

600

700

800

900

1000

Coun

ts

CKa

NK

aO

Ka

SiK

a

NiL

l NiL

a

NiK

esc

NiK

a

NiK

b

CuLl

CuLa

CuK

a

CuK

b

5 nm1

2

1

2

section S4. XRD diffraction patterns and data (figs. S6 to S10)

5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100

rela

tive

in

ten

sity /

a.u

.

2 /°

Ni@SiO2-1000

Ni-phen@SiO2-800

Ni-phen@SiO2-600

Ni

fig. S6. Powder pattern of nickel-based catalysts supported on fumed silica:

Ni@SiO2-1000 and Ni-phen@SiO2-600 show the presence of Ni(0) metal, whereas

Ni@SiO2-800 shows a slight shift to higher 2θ(°) due to the formation of silicon-poor

Ni17Si3 phase.

40 60 80 100 120 140

rela

tive inte

nsity / a

.u.

2 /°

Ni17

Si3

Ni-phen@SiO2-800

fig. S7. Powder pattern of Ni-phen@SiO2-800 measured up to 148°2θ.

5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80

Ni-NH3@SiO

2-1000

Ni-pyr@SiO2-1000

Ni-TMEDA@SiO2-1000

rela

tive

in

ten

sity /

a.u

.

2 /°

Ni@SiO2-1000

fig. S8. Powder pattern of various nickel-based catalysts with different ligands

(S2.3): Ni@SiO2-1000, Ni-NH3@SiO2-1000, and Ni-pyr@SiO2-1000 have Ni(0) metal

as the main phase. Ni-TMEDA@SiO2-1000 shows a slight shift to higher 2θ(°) which is

attributed to the formation of a Ni3Si phase.

5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80

Ni

CeO2

TiO2 (Rutile)

TiO2 (Anatase)

Ni-phen@TiO2-800

Ni-phen@CeO2-1000

Ni@SiO2-1000

rela

tive

in

ten

sity /

a.u

.

2 /°

fig. S9. Powder pattern of various nickel-based catalysts on various supports.

5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80

Ni31

Si12

Ni3Si

Ni

Ni-phen@quartz-1000

Ni-phen@SilicaGel-100

rela

tive

in

ten

sity /

a.u

.

2 /°

fig. S10. Powder pattern of nickel catalyst on silica gel and quartz (S2.3).

section S5. XPS spectra and data (fig. S11)

92 94 96 98 100 102 104 106 108 110 276278280282284286288290 526528530532534536538

835840845850855860865870875880885890390392394396398400402404406408

O 1s

Niphen@SiO21000

Si 2p

Ni 2p1/2

N 1s

C 1s

Inte

nsity / a

.u.

Inte

nsity / a

.u.

Binding Energy / eVIn

ten

sity / a

.u.

Binding Energy / eV

Inte

nsity / a

.u.

Binding Energy / eV

Inte

nsity /

a.u

.

Binding Energy / eV Binding Energy / eV

fig. S11. XPS measurement of the intermetallic nickel silicide catalyst.

section S6. Elemental analysis of the catalysts and BET (fig. S12)

table S1. Elemental analysis of the studied catalysts.

Catalyst Ni / % N / % C / %

Ni-Phen@SiO2-600 3.51 2.71 14.61

Ni-Phen@SiO2-800 3.65 1.03 14.27

Ni-Phen@SiO2-1000 3.51 0.37 13.635

Ni@ SiO2-1000 4.53 0 0.06

fig. S12. N2 adsorption-desorption isotherms and BJH desorption pore size distribution.

0 10 20 30 40 50

0.00

0.05

0.10

0.15

0.20

0.25

Pore Width (nm)

dV

/dlo

g(w

) P

ore

Volu

me (

cm

³/g) Ni-Phen@SiO2-1000

BJH Desorption dV/dlog(w) Pore Volume

BJH Desorption dA/dlog(w) Pore Area

0

50

100

150

200

250

dA

/dlo

g(w

) P

ore

Are

a (

m²/

g)

0.0 0.2 0.4 0.6 0.8 1.0

0

20

40

60

80

100

Ni-Phen@SiO2-1000

Adsorption

Desorption

Qu

an

tity

Ad

so

rbed

(cm

³/g

ST

P)

Relative Pressure (P/P0)

0.0 0.2 0.4 0.6 0.8 1.0

0

20

40

60

80

100

SiO2 treated at 1000°C

Adsorption

Desorption

Qu

an

tity

Ad

so

rbed

(cm

³/g

ST

P)


0 10 20 30 40 50

0.00

0.05

0.10

0.15

0.20

0.25

SiO2 treated at 1000°C



Pore Width (nm)

dV

/dlo

g(w

) P

ore

Vo

lum

e (

cm

³/g)

0

50

100

150

200

250

dA

/dlo

g(w

) P

ore

Are

a (

m²/

g)

0.0 0.2 0.4 0.6 0.8 1.0

0

20

40

60

80

100

Quantity

Adsorb

ed (

cm

³/g S

TP

)


Phen@SiO2-1000

Adsorption

Desorption

0 10 20 30 40 50

0.00

0.05

0.10

0.15

0.20

0.25

Phen@SiO2-1000



Pore Width (nm)

dV

/dlo

g(w

) P

ore

Vo

lum

e (

cm

³/g)

0

50

100

150

200

250

dA

/dlo

g(w

) P

ore

Are

a (

m²/

g)

table S2. BET surface area and pore volume of the samples.

Sample BET surface area (m2/g) Pore volume (cm3/g)

Ni-Phen@SiO2-1000 70.40* 0.1035

SiO2 - 1000 49.80 0.1011

Phen@SiO2-1000 48.95 0.1135

* t-Plot Micropore Area: 43.73 m²/g; t-Plot External Surface Area: 26.67 m²/g

section S7. Thermogravimetric analysis (TGA; figs. S13 and S14)

fig. S13. TG-DSC-MS analysis of Ni-phen@SiO2-1000: The sample was gradually

heated (10°C/min) to 1000°C and kept at this temperature for additional 2 hours.

TG-DSC-MS

fig. S14. TG-DSC-MS analysis of Ni-phen@SiO2-1000: The sample (27.3 mg; Al

crucible) was gradually heated in He (20 ml/min) with 5°C/min to 800°C.

section S8. Procedures for hydrogenation reactions (figs. S15 and S16)

fig. S15. Autoclave and glass vials used for hydrogenations.

Hydrogenation of nitroarenes (Procedure A). Hydrogenation of nitrobenzene: An 8

mL glass vial (Ø – 14 mm, height 50 mm) equipped with a Teflon-coated oval magnetic

stirring bar (8 × 5 mm) and a plastic screw cap was charged with nitrobenzene (51 µl, 0.5

mmol, 1.0 equiv.), 40 mg of nickel-based catalyst (~4 mol% Ni), 1 mL of deionized

water and 1 mL of methanol. The silicone septum was punctured with a 26 gauge syringe

needle (0.45 × 12 mm) and the vial was placed in the aluminum plate which was then

transferred into the 300 mL autoclave. Once sealed, the autoclave was placed into an

aluminum block and purged 3 times with hydrogen (at 5-10 bar). Then it was pressurized

to 10 bar, heated up and kept at 40°C under thorough stirring (700 rpm). After 16 h, the

autoclave was removed from the aluminum block and cooled to room temperature in a

water bath. The remaining hydrogen was discharged and the vails containing reaction

products were removed from the autoclave. To the crude reaction mixture 100 µL of n-

hexadecane (internal standard) was added, followed by the addition of 6 mL of ethyl

acetate. The resulting mixture was intensively stirred for 30 seconds and then the solid

catalyst was separated by centrifugation and the liquid phase was subjected to GC

analysis. (Note: other substrates were hydrogenated at 60°C).

Hydrogenation of aromatic ketones (Procedure B). Hydrogenation of acetophenone:

Hydrogenation was performed according to the general procedure A using acetophenone

(58 µL, 0.5 mmol, 1.0 equiv.), 45 mg of nickel-based catalyst (~4.5 mol% Ni), 2 mL of

MeOH, at 100°C, 50 bar H2, 16h.

Hydrogenation of aromatic nitriles (Procedure C). Hydrogenation of benzonitrile:

Hydrogenation was performed according to the general procedure A using benzonitrile

(51.5 µL, 0.5 mmol, 1.0 equiv.), 45 mg of nickel-based catalyst (~4.5 mol% Ni), 2 mL of

7N NH3 solution in MeOH, at 100°C, 50 bar H2, 16h.

Hydrogenation of aliphatic nitriles (Procedure D). Hydrogenation of propionitrile:

Hydrogenation was performed according to the general procedure A using benzonitrile

(35 µL, 0.5 mmol, 1.0 equiv.), 45 mg of nickel-based catalyst (~4.5 mol% Ni), 2 mL of

7N NH3 solution in MeOH, at 130°C, 50 bar H2, 16h.

Hydrogenation of aldehydes (Procedure E). Hydrogenation of m-chlorobenzaldehyde:

Hydrogenation was performed according to the general procedure A using m-

chlorobenzaldehyde (57 µL, 0.5 mmol, 1.0 equiv.), 45 mg of nickel-based catalyst (~4.5

mol% Ni), 2 mL of 1:1 MeOH/H2O, at 80°C, 20 bar H2, 16h.

Hydrogenation of alkenes and alkynes (Procedure F). Hydrogenation of 1-octene:

Hydrogenation was performed according to the general procedure A using 1-octene (78

µL, 0.5 mmol, 1.0 equiv.), 40 mg of nickel-based catalyst (~4.0 mol% Ni), 2 mL of 1:1

MeOH/H2O, at 40°C, 10 bar H2, 16h

Hydrogenation of quinolines (Procedure G). Hydrogenation of quinaldine:

Hydrogenation was performed according to the general procedure A using quinaldine (68

µL, 0.5 mmol, 1.0 equiv.), 45 mg of nickel-based catalyst (~4.5 mol% Ni), 2 mL of 1:1

MeOH/H2O, at 120°C, 50 bar H2, 16h

table S3. Hydrogenation of the standard substrates (Table 1 in the main text). Catalysts were prepared from Ni(Phen)2(AcO)2 according to the procedure S2.2. and the

names below the chart reflect the support and pyrolysis temperatures. Green –

Nitrobenzene; Red – Acetophenone; Blue – Benzonitrile. GC conversion using n-

hexadecane standard.

C

-600

C-8

00

C-1

000

SiC

-600

SiC

-800

SiC

-1000

TIO

2-6

00

TIO

2-8

00

TIO

2-1

000

CeO

2-6

00

CeO

2-8

00

CeO

2-1

000

SiO

2-6

00

SiO

2-8

00

SiO

2-1

000

Al2

O3-6

00

Al2

O3-8

00

Al2

O3-1

000

0

10

20

30

40

50

60

70

80

90

100

Co

nv., %

table S4. Hydrogenation of the nitrobenzene with SiO2-supported catalysts:

Materials were prepared from Ni(AcO)2∙4H2O and a corresponding ligand (2.0 or 4.0

equiv.) according to the procedure S2.3. The names below the chart reflect the support,

ligand and pyrolysis temperatures. GC conversion using n-hexadecane standard.

SiO

2-

NL-6

00

SiO

2-N

L-8

00

SiO

2-

NL-1

000

SiO

2-P

yr-

600

SiO

2-P

yr-

800

SiO

2-P

yr-

1000

SiO

2-T

ME

DA

-600

SiO

2-T

ME

DA

-800

SiO

2-T

ME

DA

-1000

SiO

2-N

H3-8

00

SiO

2-N

H3-1

000

quart

z-p

hen-1

000

SilG

el-phen-1

000

SiO

2-p

hen-1

000

0

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20

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40

50

60

70

80

90

100

Co

nv., %

Hot filtration test.

To confirm the heterogeneous character of the catalyst, a hot filtration test was performed

during hydrogenation of benzonitrile (procedure C). After 4 h the reaction was stopped,

the autoclave was cooled to 60°C and degassed. Hot reaction mixture was quickly filtered

through a short Celite plug (~2 cm) preheated with a heat gun to 60°C. The resulting

mixture was analyzed by GC, giving 42% conversion. This mixture was place back in an

autoclave and subjected to standard hydrogenation condition was additional 16h.

Analysis of the resulting reaction mixture revealed that no further hydrogenation was

observed.

0 1 2 3 4 5 6 7 8 9 10

0

10

20

30

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50

60

70

80

90

100

yie

ld, %

time, h

fig S16. Concentration/time diagram for the hydrogenation of benzonitrile. Hydrogenation was performed according to the general procedure C and stopped at a

certain time. The resulting mixture was analyzed by GC, using n-hexadecane as internal

standard. For every time point a new reaction was performed and every data point is an

average of two runs.

section S9. Product characterization

4-Aminobenzophenone. Hydrogenation of 4-nitrobenzophenone (113 mg, 0.5 mmol) according to the procedure

A afforded the title compound as a yellow solid (78 mg, 79%).

1H NMR (300 MHz, Chloroform-d) δ 7.76 – 7.67 (m, 4H), 7.58 – 7.49 (m, 1H), 7.49 –

7.38 (m, 2H), 6.73 – 6.56 (m, 2H), 4.24 (br. s, 2H). 13C NMR (75 MHz, CDCl3) δ 195.4, 151.2, 138.9 , 133.0 (+), 131.5 (+), 129.5 (+), 128.1

(+), 127.3, 113.6 (+).

Methyl 2-aminobenzoate.

Hydrogenation of methyl 2-nitrobenzoate (70 µL, 0.5 mmol) according to the procedure

A afforded the title compound as a yellow oil (57 mg, 75%).

1H NMR (300 MHz, Chloroform-d) 7.90 (dd, J = 8.2, 1.3 Hz, 1H), 7.31 (ddd, J = 8.2, 7.3,

1.6 Hz, 1H), 6.70 (td, J = 8.1, 1.0 Hz, 2H), 5.87 (br. s, 2H), 3.92 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 168.6, 150.4, 134.1 (+), 131.2 (+), 116.7 (+), 116.3 (+),

110.8, 51.6 (+).

Benzene-1,2-diamine.

Hydrogenation of 2-nitroaniline (48 µL, 0.5 mmol) according to the procedure A

afforded the title compound as a brown solid (54 mg, 99%).

1H NMR (300 MHz, Chloroform-d) δ 6.72 (m, 4H), 3.40 (br. s, 4H). 13C NMR (75 MHz, CDCl3) δ 134.8, 120.4 (+), 116.8 (+).

2-Ethoxyaniline.

Hydrogenation of 2-ethoxynitrobenzene (70.5 µL, 0.5 mmol) according to the procedure

A afforded the title compound as a yellow oil (55 mg, 80%).

1H NMR (300 MHz, Chloroform-d) δ 6.93 – 6.60 (m, 4H), 4.07 (q, J = 7.0 Hz, 2H), 3.80

(br. s, 2H), 1.44 (t, J = 7.0 Hz, 3H). 13C NMR (75 MHz, CDCl3) δ 146.7, 136.4, 121.1 (+), 118.6 (+), 115.2 (+), 111.6 (+),

63.8 (–), 15.1 (+).

2-Bromo-3-methylaniline.

Hydrogenation of 2-bromo-3-methylnitrobenzene (108 mg, 0.5 mmol) according to the

procedure A afforded the title compound as yellow oil (75 mg, 80%).

1H NMR (300 MHz, Chloroform-d) δ 7.01 (t, J = 7.6 Hz, 1H), 6.73 – 6.52 (m, 2H), 3.87

(br. s, 1H), 2.37 (s, 3H). 13C NMR (75 MHz, CDCl3) 144.1, 138.7, 127.4 (+), 120.5 (+), 113.4 (+), 112.5, 23.7

(+).

2-Aminobenzamide.

Hydrogenation of 2-amidonitrobenzene (108 mg, 0.5 mmol) according to the procedure

A afforded the title compound as a yellow solid (55 mg, 81%).

1H NMR (300 MHz, Chloroform-d) δ 7.36 (dd, J = 8.0, 1.5 Hz, 1H), 7.28 – 7.16 (m, 1H),

6.73 – 6.56 (m, 2H), 6.09 (br. s, 2H), 5.80 (br. s, 2H). 13C NMR (75 MHz, CDCl3) δ 172.1, 149.5, 133.2 (+), 128.1 (+), 117.6 (+), 116.5 (+),

114.0.

N-(4-Aminophenyl)benzamide.

Hydrogenation of N-(4-nitrophenyl)benzamide (121 mg, 0.5 mmol) according to the

procedure A afforded the title compound as a brown solid (105 mg, 99%).

1H NMR (300 MHz, Methanol-d4) δ 7.99 – 7.81 (m, 2H), 7.61 – 7.43 (m, 3H), 7.42 –

7.34 (m, 2H), 6.80 – 6.69 (m, 2H). 13C NMR (75 MHz, MeOD) δ 168.6, 146.0, 136.3, 132.6 (+), 130.4, 129.5 (+), 128.4 (+),

124.2 (+), 116.6 (+).

1-(7-Amino-5-bromoindolin-1-yl)ethan-1-one.

Hydrogenation of 1-(5-bromo-7-nitroindolin-1-yl)ethan-1-one (143 mg, 0.5 mmol)

according to the procedure A afforded the title compound as a grey solid (118 mg, 93%).

1H NMR (300 MHz, Chloroform-d) δ 6.66 (br. s, 2H), 4.80 (br. s, 2H), 3.99 (t, J = 7.8

Hz, 2H), 2.94 (br. s, 2H), 2.28 (br. s, 3H). 1H NMR (300 MHz, Methanol-d4) δ 6.84 (s, 1H), 6.78 (s, 1H), 4.12 (t, J = 7.8 Hz, 2H),

3.04 (t, J = 7.7 Hz, 2H), 2.33 (s, 3H). 1H NMR (300 MHz, DMSO-d6) δ 6.76 (d, J = 2.0 Hz, 1H), 6.66 (dt, J = 2.0, 1.0 Hz, 1H),

5.59 (br. s, 2H), 4.02 (dd, J = 8.2, 7.6 Hz, 2H), 2.95 (dd, J = 8.5, 7.1 Hz, 2H), 2.21 (s,

3H). 13C NMR (75 MHz, DMSO-d6) δ 168.3, 140.2, 138.2, 128.1, 118.1, 117.8 (+), 115.6 (+),

51.2, 40.0 (–), 29.2 (–), 24.5 (+).

4-(Methylthio)aniline. Hydrogenation of 4-(methylthio)nitrobenzene (85 mg, 0.5 mmol) according to the

procedure A afforded the title compound as a red oil (70 mg, 99%).

1H NMR (300 MHz, Chloroform-d) δ 7.24 – 7.13 (m, 2H), 6.78 – 6.48 (m, 2H), 3.61

(br.s, 2H), 2.41 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 145.1, 131.0 (+), 125.8 (+), 115.8, 18.8 (+).

3,4,5-Trichloroaniline.

Hydrogenation of 3,4,5-trichloronitrobenzene (113 mg, 0.5 mmol) according to the

procedure A afforded the title compound as a white-grey solid (91 mg, 94%).

1H NMR (300 MHz, Chloroform-d) δ 6.67 (s, 2H), 3.77 (br. s, 2H). 13C NMR (75 MHz, CDCl3) δ 145.8, 134.3, 119.9, 115.1 (+).

3-Aminopyridine

Hydrogenation of 3-nitropyridine (62 mg, 0.5 mmol) according to the procedure A

afforded the title compound as a pale yellow solid (46 mg, 98%).

1H NMR (300 MHz, Chloroform-d) δ 8.03 (m, 2H), 7.18 – 6.82 (m, 2H), 3.77 (br. s, 2H). 13C NMR (75 MHz, CDCl3) δ 142.7, 140.0 (+), 137.5 (+), 123.8 (+), 121.4 (+).

4-Aminophenol

Hydrogenation of 4-nitrophenol (70 mg, 0.5 mmol) according to the procedure A


1H NMR (300 MHz, DMSO-d6) δ 8.36 (br. s, 1H), 6.53 – 6.46 (m, 2H), 6.46 – 6.38 (m,

2H), 4.37 (br. s, 2H). 13C NMR (75 MHz, DMSO-d6) δ 148.3, 140.7, 115.6 (+), 115.3 (+).

Benzo[c][1,2,5]thiadiazol-4-amine

Hydrogenation of 4-nitrobenzo[c][1,2,5]thiadiazole (90 mg, 0.5 mmol) according to the

procedure A afforded the title compound as a yellow solid (52 mg, 69%).

1H NMR (300 MHz, Chloroform-d) δ 7.47 – 7.29 (m, 2H), 6.60 (dd, J = 6.8, 1.3 Hz, 1H),

4.69 (br. s, 2H). 13C NMR (75 MHz, CDCl3) δ 155.9, 147.9, 139.0, 131.3 (+), 110.1 (+), 106.7 (+).

4-Aminoacetphenone.

Hydrogenation of 4-nitroacetophenone (82 mg, 0.5 mmol) according to the procedure A

afforded the title compound as a white solid (67 mg, 99%).


4.17 (br. s, 2H), 2.49 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 196.6, 151.3, 130.8 (+), 127.7, 113.7 (+), 26.1 (+).

4-Phenoxyaniline.

Hydrogenation of 4-phenoxynitrobenzene (108 mg, 0.5 mmol) according to the procedure

A afforded the title compound as a brown oil (90 mg, 97%).


6.96 (m, 2H), 6.95 – 6.88 (m, 2H), 6.78 – 6.63 (m, 2H), 3.63 (br. s, 2H). 13C NMR (75 MHz, CDCl3) δ 159.0, 148.6, 142.8, 129.6 (+), 122.1 (+), 121.2 (+), 117.3

(+), 116.3 (+).

Dimethyl 5-aminoisophthalate.

Hydrogenation of dimethyl 5-nitroisophthalate (120 mg, 0.5 mmol) according to the

procedure A afforded the title compound as a white solid (104 mg, 99%).

1H NMR (300 MHz, Chloroform-d) δ 8.04 (t, J = 1.5 Hz, 1H), 7.51 (d, J = 1.5 Hz, 2H),

3.97 – 3.93 (br. s, 2H), 3.90 (s, 6H). 13C NMR (75 MHz, CDCl3) δ 166.6, 146.9, 131.6, 120.7 (+), 119.9 (+), 52.4 (+).

4-Methylbenzene-1,3-diamine.

Hydrogenation of 1-methyl-2,4-dinitrobenzene (91 mg, 0.5 mmol) according to the

procedure A with doubled catalyst loading (80 mg Ni-Phen@SiO2-1000, 8 mol% Ni)


1H NMR (300 MHz, Chloroform-d)δ 6.88 – 6.75 (m, 1H), 6.10 (dd, J = 7.8, 2.3 Hz, 1H),

6.05 (d, J = 2.3 Hz, 1H), 3.49 (br. s, 4H), 2.29 – 1.82 (m, 3H). 13C NMR (75 MHz, CDCl3) δ 145.6, 145.3, 131.1 (+), 112.9, 106.0 (+), 102.2 (+), 16.5

(+).

Benzene-1,2-diamine.

Hydrogenation of 1,2,-dinitrobenzene (94 mg, 0.5 mmol) according to the procedure A

with doubled catalyst loading (80 mg Ni-Phen@SiO2-1000, 8 mol% Ni) afforded the title

compound as a brown solid (52 mg, 96%). 1H NMR (300 MHz, Chloroform-d) δ 6.73 (m, 4H), 3.39 (br. s, 4H). 13C NMR (75 MHz, CDCl3) δ 134.8, 120.3 (+), 116.8 (+).

5-Aminoindole.

Hydrogenation of 5-nitroindole (81 mg, 0.5 mmol) according to the procedure A at 80°C

and 20 bar H2 afforded the title compound as a brown solid (67 mg, 98%).

1H NMR (300 MHz, Chloroform-d) δ 7.98 (br. s, 1H), 7.19 (dt, J = 8.5, 0.8 Hz, 1H), 7.12

(dd, J = 3.2, 1.7 Hz, 1H), 6.95 (dd, J = 2.3, 0.6 Hz, 1H), 6.67 (ddd, J = 8.5, 2.2, 0.5 Hz,

1H), 6.38 (dd, J = 2.9, 1.4 Hz, 1H), 3.49 (br. s, 2H). 13C NMR (75 MHz, CDCl3) δ 139.7, 130.8, 128.9, 124.8 (+), 113.1 (+), 111.6 (+), 105.7

(+), 101.7 (+).

1-Phenylethanol.

Hydrogenation of acetophenone (58µL, 0.5 mmol) according to the procedure B afforded

the title compound as a yellow oil (61 mg, 99%).

1H NMR (300 MHz, Chloroform-d) δ 7.38 – 7.23 (m, 4H), 7.29 – 7.17 (m, 1H), 4.85 (q, J

= 6.5 Hz, 1H), 2.03 (br. s, 1H), 1.46 (dd, J = 6.5, 1.5 Hz, 3H). 13C NMR (75 MHz, CDCl3) δ145.9, 128.6 (+), 127.6 (+), 125.5 (+), 125.1, 70.5 (+), 25.3

(+).

2,2,2-Trifluoro-1-phenylethan-1-ol. Hydrogenation of 2,2,2-trifluoroacetophenone (58µL, 0.5 mmol) according to the

procedure B afforded the title compound as a colorless oil (65 mg, 74%).

1H NMR (300 MHz, Chloroform-d) δ 7.63 – 7.18 (m, 5H), 4.99 (q, J = 6.7 Hz, 1H), 2.92

(br s, 1H). 13C NMR (75 MHz, CDCl3) δ 134.1, 129.7 (+), 128.8 (+), 127.6 (+), 124.4 (d, J = 282.1

Hz), 72.9 (q, J = 31.9 Hz) (+). 19F NMR (282 MHz, Chloroform-d) δ -77.92 (d, J = 6.9 Hz).

1-(Pyridin-4-yl)ethan-1-ol.

Hydrogenation of 4-acetylpyridine (60 mg, 0.5 mmol) according to the procedure B

afforded the title compound as a yellow oil (55 mg, 88%).

1H NMR (400 MHz, Chloroform-d) δ 8.40 (d, J = 4.6 Hz, 2H), 7.59 – 6.87 (m, 2H), 4.88

(q, J = 6.5 Hz, 1H), 1.48 (d, J = 6.5 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 156.0, 149.2 (+), 120.7 (+), 68.4 (+), 25.1 (+).

1,2-Diphenylethan-1-ol.

Hydrogenation of 2-phenylacetophenone (98 mg, 0.5 mmol) according to the procedure

B afforded the title compound as a white solid (96 mg, 97%).

1H NMR (300 MHz, Methanol-d4) δ 7.39 – 7.00 (m, 10H), 4.96 (br. s, 1H), 4.86 (dd, J

= 7.3, 6.3 Hz, 1H), 3.08 (dd, J = 13.4, 7.4 Hz, 1H), 2.98 (dd, J = 13.4, 6.3 Hz, 1H). 13C NMR (75 MHz, Methanol-d4) δ 145.6, 139.7, 133.7 (+), 130.6 (+), 129.1 (+), 129.0

(+), 128.2 (+), 127.2 (+), 127.1 (+), 76.5 (+), 46.9 (–).

1-(Pyridin-2-yl)ethan-1-ol.

Hydrogenation of 2-acetylpyridine (60 mg, 0.5 mmol) according to the procedure B


1H NMR (300 MHz, Chloroform-d) δ 8.50 (ddd, J = 5.0, 1.7, 1.0 Hz, 1H), 7.66 (ddd, J =

7.9, 7.5, 1.8 Hz, 1H), 7.28 (d, J = 7.9 Hz, 1H), 7.17 (dddd, J = 7.5, 4.9, 1.1, 0.5 Hz, 1H),

4.87 (q, J = 6.5 Hz, 1H), 4.18 (br. s, 1H), 1.48 (d, J = 6.6 Hz, 3H). 13C NMR (75 MHz, CDCl3) δ 163.2, 148.2 (+), 136.9 (+), 122.3 (+), 119.9 (+), 69.0 (+),

24.3 (+).

1-(4-Ethylphenyl)ethan-1-ol.

Hydrogenation of 4’-ethylacetophenone (74 µL, 0.5 mmol) according to the procedure B


1H NMR (300 MHz, Chloroform-d) δ. 7.31 (d, J = 8.1 Hz, 2H), 7.21 (d, J = 8.3 Hz, 2H),

4.87 (q, J = 6.5 Hz, 1H), 2.68 (q, J = 7.6 Hz, 2H), 2.21 (br. s, 1H), 1.50 (d, J = 6.5 Hz,

3H), 1.27 (t, J = 7.6 Hz, 3H). 13C NMR (75 MHz, CDCl3) δ 143.4, 143.1, 127.9 (+), 125.4 (+), 70.1 (+), 28.5 (–), 25.0

(+), 15.6 (+).

1,1'-(1,4-Phenylene)bis(ethan-1-ol).

Hydrogenation of 1,4-diacetylbenzene (81 mg, 0.5 mmol) according to the procedure B

with doubled catalyst loading (90 mg Ni-Phen@SiO2-1000, 9.0 mol% Ni) afforded the

title compound as a white solid (78 mg, 94%).

1H NMR (300 MHz, Chloroform-d) δ 7.19 (s, 4H), 4.72 (q, J = 6.5 Hz, 2H), 2.67 (br. s,

2H), 1.35 (d, J = 6.5 Hz, 6H). 13C NMR (75 MHz, CDCl3) δ 144.9, 125.4 (+), 69.88 (+), 69.86 (+), 25.0 (+).

1-Phenylpropan-1-ol.

Hydrogenation of propiophenone (66 µL, 0.5 mmol) according to the procedure B

afforded the title compound as a colorless oil (55 mg, 81%).

1H NMR (300 MHz, Chloroform-d) δ 7.47 – 7.24 (m, 5H), 4.62 (dd, J = 7.0, 6.2 Hz, 1H),

2.22 (br. s, 1H), 1.99 – 1.64 (m, 2H), 0.97 (t, J = 7.4 Hz, 3H). 13C NMR (75 MHz, CDCl3) δ 144.5, 128.3 (+), 127.4 (+), 125.9 (+), 75.9 (+), 31.8 (–),

10.1 (+).

144.9, 125.4 (+), 69.88 (+), 69.86 (+), 25.0 (+).

1,2-diphenylethane-1,2-diol

Hydrogenation of benzil (105 mg, 0.5 mmol) according to the procedure B with doubled

catalyst loading (90 mg Ni-Phen@SiO2-1000, 9.0 mol% Ni) afforded the title compound

as a white solid (100 mg, 93%).


6.96 (m, 2H), 4.76 (s, 2H) (anti), 4.62 (s, 1H) (syn), 2.97 (s, 1H) (syn), 2.33 (s, 2H) (anti). 13C NMR (75 MHz, CDCl3) δ 139.8 (syn), 139.7 (anti), 128.2 (+)(anti), 128.1 (+) (syn),

128.0 (+) (syn), 127.9 (+) (syn), 127.0 (+)(anti), 126.9 (+) (anti), 79.0 (+) (syn), 78.0

(anti) (+).


Hydrogenation of 3-phenylpropanal (66 µL, 0.5 mmol) according to the procedure E


1H NMR (300 MHz, Chloroform-d) δ 7.37 – 7.27 (m, 2H), 7.25 – 7.17 (m, 3H), 3.68 (t, J

= 6.5 Hz, 2H), 2.78 – 2.67 (m, 2H), 1.99 – 1.84 (m, 2H), 1.79 (br. s, 1H).

δ 7.47 – 7.24 (m, 5H), 4.62 (dd, J = 7.0, 6.2 Hz, 1H), 2.22 (br. s, 1H), 1.99 – 1.64 (m,

2H), 0.97 (t, J = 7.4 Hz, 3H). 13C NMR (75 MHz, CDCl3) δ 141.9, 128.5 (+), 128.5 (+), 125.9(+), 62.3 (–), 34.3 (–),

32.2 (–).

(2-Chlorophenyl)methanamine.

Hydrogenation of 2-chlorobenzonitrile (69 mg, 0.5 mmol) according to the procedure C


1H NMR (300 MHz, Chloroform-d) δ 7.28 (ddd, J = 7.1, 4.5, 1.7 Hz, 2H), 7.13 (dtd, J =

17.1, 7.4, 1.7 Hz, 2H), 3.84 (s, 2H), 1.70 (s, 2H). 13C NMR (75 MHz, CDCl3) δ 140.6, 133.4, 129.6 (+), 129.0 (+), 128.3 (+), 127.2 (+),

44.6 (–).

4-(Aminomethyl)-N,N-dimethylaniline. Hydrogenation of 4-(N,N-dimethyl)aminobenzonitrile (73 mg, 0.5 mmol) according to

the procedure C afforded the title compound as a yellow oil (67 mg, 90%).

1H NMR (300 MHz, Chloroform-d) δ 7.19 (d, J = 8.9 Hz, 2H), 6.73 (d, J = 8.6 Hz, 2H),

3.76 (s, 4H), 2.93 (s, 6H). 13C NMR (75 MHz, CDCl3) δ 149.8, 131.6, 128.1 (+), 113.0 (+), 46.1 (–), 40.9 (–).

(6-Methoxypyridin-3-yl)methanamine.

Hydrogenation of 6-methoxynicotinonitrile (67 mg, 0.5 mmol) according to the

procedure C afforded the title compound as a yellow oil (68 mg, 99%).

1H NMR (300 MHz, Chloroform-d) δ 8.15 – 7.94 (m, 1H), 7.55 (ddd, J = 8.5, 2.4, 0.6 Hz,

1H), 6.71 (dd, J = 8.5, 0.8 Hz, 1H), 3.91 (s, 3H), 3.79 (s, 2H). 13C NMR (75 MHz, CDCl3) δ 163.4, 145.4 (+), 138.2 (+), 131.1, 110.8 (+), 53.4 (+), 43.4

(–).

(4-Methoxyphenyl)methanamine.

Hydrogenation of 4-methoxybenzonitrile (66.5 mg, 0.5 mmol) according to the procedure

C afforded the title compound as a yellow oil (60 mg, 87%).

1H NMR (300 MHz, Chloroform-d) δ 7.22 (d, J = 8.5 Hz, 2H), 6.86 (d, J = 8.6 Hz, 3H),

3.79 (br. s, 5H), 1.66 (br. s., 2H). 13C NMR (75 MHz, CDCl3) δ 158.6, 135.7, 128.3 (+), 114.0 (+), 55.38 (+), 46.01 (–).

(6-methoxynaphthalen-2-yl)methanamine.

Hydrogenation of 6-methoxy-2-naphthonitrile (92 mg, 0.5 mmol) according to the

procedure C afforded the title compound as a white solid (94 mg, 99%).

1H NMR (300 MHz, Chloroform-d). 7.78 – 7.61 (m, 3H), 7.40 (dd, J = 8.4, 1.8 Hz, 1H),

7.14 (d, J = 8.5 Hz, 1H), 7.13 (s, 1H), 3.99 (s, 2H), 3.91 (s, 3H). 13C NMR (75 MHz, CDCl3) 157.5, 138.6, 133.7, 129.2 (+), 129.1 (+), 127.2 (+), 126.5

(+), 125.1 (+), 118.9 (+), 105.8 (+), 55.4 (+), 46.6 (–).

(1H-Indol-4-yl)methanamine.

Hydrogenation of 1H-indole-4-carbonitrile (71 mg, 0.5 mmol) according to the procedure

C afforded the title compound as a yellow solid (69 mg, 95%).

1H NMR (300 MHz, Chloroform-d). δ 8.57 (br. s, 1H), 7.31 (d, J = 8.4 Hz, 1H), 7.24 –

7.15 (m, 2H), 7.08 (d, J = 7.1 Hz, 1H), 6.63 (t, J = 3.1 Hz, 1H), 4.21 (br. s, 2H), 1.57

(br.s, 2H). 13C NMR (75 MHz, CDCl3), δ 136.0, 126.2, 125.1, 124.2 (+), 122.3 (+), 117.6 (+), 110.1

(+), 100.4 (+), 44.6 (–).

4-Aminobenzylamine.

Hydrogenation of 4-aminobenzonitrile (59 mg, 0.5 mmol) according to the procedure C

afforded the title compound as a yellow solid (61 mg, 99%).

1H NMR (300 MHz, Chloroform-d). δ 7.09 (d, J = 7.9 Hz, 2H), 6.65 (d, J = 7.9 Hz, 2H),

3.82 (s, 2H), 3.64 (br. s, 2H) 1.74 – 1.15 (br. s, 2H). 13C NMR (75 MHz, CDCl3), δ 145.3, 129.4, 128.3 (+), 115.3 (+), 45.9 (–).

p-Tolylmethanamine hydrochloride.

Hydrogenation of 4-methylbenzonitrile (59 mg, 0.5 mmol) according to the procedure C

and subsequent treatment with HCl in ether afforded the title compound as a white solid

(67 mg, 85%).

1H NMR (400 MHz, Methanol-d4) δ 7.38 (d, J = 8.1 Hz, 2H), 7.25 (d, J = 7.9 Hz, 2H),

4.87 (br. s, 3H), 4.08 (s, 2H), 2.34 (s, 3H). 13C NMR (101 MHz, MeOD) δ 140.2, 131.4, 130.7 (+), 130.1 (+), 44.1 (–), 21.2 (+).

[1,1'-Biphenyl]-4-ylmethanamine hydrochloride.

Hydrogenation of 4-phenylbenzonitrile (89.5 mg, 0.5 mmol) according to the procedure

C and subsequent treatment with HCl in ether afforded the title compound as a white

solid (108 mg, 98%).

1H NMR (300 MHz, Methanol-d4) δ 7.83 – 7.75 (m, 2H), 7.74 – 7.68 (m, 2H), 7.64 (dt, J

= 8.1, 1.2 Hz, 2H), 7.59 – 7.49 (m, 2H), 7.47 – 7.39 (m, 1H), 4.98 (s, 3H), 4.25 (s, 2H). 13C NMR (75 MHz, MeOD) δ 143.3, 141.4, 133.3, 130.6 (+), 130.0 (+), 128.8 (+), 128.7

(+), 128.0 (+), 44.0 (–).

(4-Chlorophenyl)methanamine hydrochloride.

Hydrogenation of 4-chlorobenzonitrile (69 mg, 0.5 mmol) according to the procedure C


(73 mg, 82%).

1H NMR (400 MHz, Methanol-d4) 7.57 – 7.52 (m, 2H), 7.51 – 7.45 (m, 2H), 4.91 (s,

3H), 4.18 (s, 2H). 13C NMR (101 MHz, MeOD) δ 136.1, 133.2, 131.9 (+), 130.2 (+), 43.6 (–).

4-(aminomethyl) hydrochloride.

Hydrogenation of 4-amidobenzonitrile (73 mg, 0.5 mmol) according to the procedure C


(68 mg, 73%).


4.79 (br.s, 6H), 4.11 (s, 2H). 13C NMR (101 MHz, MeOD) δ 171.5, 138.2, 135.6, 130.1 (+), 129.4 (+), 43.8 (–).

2-(Aminomethyl)aniline dihydrochloride.

Hydrogenation of 2-aminobenzonitrile (59 mg, 0.5 mmol) according to the procedure C

and subsequent treatment with HCl in ether afforded the title compound as a yellow solid

(96 mg, 98%).

1H NMR (400 MHz, Methanol-d4) δ 7.86 – 7.69 (m, 1H), 7.66 – 7.51 (m, 3H), 5.02 (br.

s, 6H), 4.36 (s, 2H). 13C NMR (101 MHz, MeOD) δ 132.8 (+), 132.1 (+), 131.1 (+), 130.96, 128.76, 125.7,

39.13.

Benzylamine hydrochloride.

Hydrogenation of benzonitrile (51.5 µL, 0.5 mmol) according to the procedure C and

subsequent treatment with HCl in ether afforded the title compound as a white solid (65

mg, 91%).

1H NMR (400 MHz, Methanol-d4) δ 7.71 – 7.06 (m, 5H), 4.87 (s, 3H), 4.13 (s, 2H). 13C NMR (101 MHz, MeOD) δ 134.4, 130.2 (+), 130.0 (+), 44.3 (–).

1,4-Phenylenedimethanamine hydrochloride. Hydrogenation of terephthalonitrile (64 mg, 0.5 mmol) according to the procedure C,

with a doubled catalyst loading (90 mg Ni-Phen@SiO2-1000, 9.0 mol% Ni), 150°C and


mg, 76%).

1H NMR (300 MHz, Deuterium Oxide) δ 7.52 (s, 4H), 4.21 (s, 4H).

13C NMR (75 MHz, D2O) δ 133.4, 129.5 (+), 42.6 (–).

1,3-Phenylenedimethanamine dihydrochloride.

Hydrogenation of isophthalonitrile (64 mg, 0.5 mmol) according to the procedure C, with

a doubled catalyst loading (90 mg Ni-Phen@SiO2-1000, 9.0 mol% Ni), 150°C and


mg, 76%).

1H NMR (300 MHz, Methanol-d4) δ 7.64 (s, 1H), 7.60 – 7.52 (m, 3H), 4.19 (s, 4H). 13C NMR (75 MHz, MeOD) δ 135.4, 131.1 (+), 131.0 (+), 130.8 (+), 44.0 (–).

(3-(Pyrrolidin-1-yl)phenyl)methanamine hydrochloride .

Hydrogenation of 3-(pyrrolidin-1-yl)benzonitrile (86 mg, 0.5 mmol) according to the

procedure C and subsequent treatment with HCl in ether afforded the title compound as a

white solid (90 mg, 85%).

1H NMR (300 MHz, Methanol-d4) δ 7.99 – 7.89 (m, 1H), 7.77 (dt, J = 7.1, 2.2 Hz, 1H),

7.69 – 7.56 (m, 2H), 4.24 (s, 2H), 3.89 – 3.65 (m, 4H), 2.45 – 2.22 (m, 4H). 13C NMR (75 MHz, MeOD) δ 142.2, 137.1, 132.1 (+), 131.6 (+), 123.6 (+), 123.3 (+),

59.3 (–), 43.6 (–), 24.9 (–).

(4-Ethylphenyl)methanamine hydrochloride.

Hydrogenation of 4-ethylbenzonitrile (65 mg, 0.5 mmol) according to the procedure C


(80 mg, 94%).

1H NMR (300 MHz, Methanol-d4) δ 7.41 (dd, J = 8.1, 0.6 Hz, 2H), 7.30 – 7.24 (m, 2H),

4.09 (s, 2H), 2.66 (q, J = 7.6 Hz, 2H), 1.22 (t, J = 7.6 Hz, 3H). 13C NMR (75 MHz, MeOD) δ 146.7, 131.7, 130.2 (+), 129.6 (+), 44.1 (–), 29.5 (–), 16.1

(+).

(1-(4-Fluorophenyl)-1,3-dihydroisobenzofuran-5-yl)methanamine hydrochloride

Hydrogenation of 1-(4-fluorophenyl)-1,3-dihydroisobenzofuran-5-carbonitrile (120 mg,

0.5 mmol) according to the procedure C and subsequent treatment with HCl in ether



6.81 (m, 3H), 6.16 (d, J = 2.4 Hz, 1H), 5.34 (dd, J = 12.6, 2.4 Hz, 1H), 5.18 (ddt, J = 12.7,

1.9, 0.9 Hz, 1H), 4.16 (s, 2H). 13C NMR (75 MHz, MeOD) δ 164.0 (d, J = 244.8 Hz), 144.4, 141.4, 139.5 (d, J = 3.2

Hz), 134.3, 129.6 (d, J = 8.3 Hz) (+), 129.7 (+), 123.9 (+), 123.1 (+), 116.3 (d, J = 21.7

Hz) (+), 86.5 (+), 73.8 (–), 44.1 (–). 19F NMR (282 MHz, Methanol-d4) δ –115.91 (ddd, J = 13.8, 9.1, 5.4 Hz).

(4-(Benzyloxy)phenyl)methanamine hydrochloride.

Hydrogenation of 4-benzylbenzonitrile (104.5 mg, 0.5 mmol) according to the procedure


solid (120 mg, 96%).

1H NMR (300 MHz, Methanol-d4) 7.51 – 7.23 (m, 7H), 7.12 – 6.92 (m, 2H), 5.10 (s,

2H), 4.04 (s, 2H). 13C NMR (75 MHz, MeOD) δ 160.7, 138.4, 131.6 (+), 129.5 (+), 128.9 (+), 128.5 (+),

126.6, 116.5 (+), 70.9 (–), 43.8 (–).

(4-(Phenoxy)phenyl)methanamine hydrochloride. Hydrogenation of 4-phenoxybenzonitrile (97.5 mg, 0.5 mmol) according to the procedure


solid (105 mg, 89%).

1H NMR (300 MHz, Methanol-d4) δ 7.47 (d, J = 8.6 Hz, 2H), 7.41 – 7.31 (m, 2H), 7.15

(ddt, J = 7.9, 7.0, 1.1 Hz, 1H), 7.06 – 6.91 (m, 4H), 4.11 (s, 2H).

13C NMR (75 MHz, MeOD) δ 159.7, 157.9, 132.0 (+), 131.0 (+), 129.0, 125.0 (+), 120.3

(+), 119.8 (+), 43.7 (–).

Quinolin-6-ylmethanamine hydrochloride.

Hydrogenation of quinoline-6-carbonitrile (77 mg, 0.5 mmol) according to the procedure

C and subsequent treatment with HCl in ether afforded the title compound as a yellow

solid (87 mg, 89%).

1H NMR (300 MHz, Methanol-d4) δ 9.35 (d, J = 6.5 Hz, 2H), 8.64 – 8.51 (m, 1H), 8.43

(dt, J = 8.9, 0.7 Hz, 1H), 8.36 (dd, J = 8.9, 1.9 Hz, 1H), 8.28 – 8.17 (m, 1H), 4.53 (br. s,

2H), 3.35 (br. s, 2H). 13C NMR (75 MHz, MeOD) δ 149.1 (+), 146.7 (+), 138.8, 137.0, 136.9 (+), 131.0 (+),

130.4, 123.9 (+), 122.4 (+), 43.5 (–).

Naphthalen-2-ylmethanamine hydrochloride

Hydrogenation of 2-naphthonitrile (77 mg, 0.5 mmol) according to the procedure C and


mg, 89%).

1H NMR (300 MHz, Methanol-d4) δ 8.02 – 7.97 (m, 1H), 7.94 (d, J = 8.5 Hz, 1H), 7.93 –

7.85 (m, 2H), 7.57 (dd, J = 8.5, 1.8 Hz, 1H), 7.55 – 7.50 (m, 2H), 4.29 (s, 2H). 13C NMR (75 MHz, MeOD) δ 134.8, 134.7, 131.8, 130.0 (+), 129.5 (+), 129.1 (+), 128.8

(+), 127.9 (+), 127.8(+), 127.0 (+), 44.5 (–).

Methyl 4-(aminomethyl)benzoatehydrochloride. Hydrogenation of methyl 4-cyanobenzoate (80 mg, 0.5 mmol) according to the procedure

C, using 2 mL of MeOH as a solvent, and subsequent treatment with HCl in ether



4.21 (s, 2H), 3.92 (s, 3H). 13C NMR (101 MHz, MeOD) δ 167.8, 139.5, 132.0, 131.2 (+), 130.1 (+), 52.8 (+), 43.8

(–).

Heptylamine hydrochloride Hydrogenation of heptanenitrile (69 µL, 0.5 mmol) according to the procedure D and


mg, 73%).

1H NMR (300 MHz, Methanol-d4) δ 2.84 (t, J = 7.7 Hz, 2H), 1.59 (dq, J = 9.0, 7.0 Hz,

2H), 1.38 – 1.08 (m, 8H), 0.88 – 0.77 (m, 3H). 13C NMR (75 MHz, MeOD) δ 40.8 (–), 32.7 (–), 29.9 (–), 28.5 (–), 27.4 (–), 23.7 (–),

14.4 (+).

1-Cyclohexylmethanamine hydrochloride.

Hydrogenation of cyclohexanenitrile (59 µL, 0.5 mmol) according to the procedure D


(73 mg, 97%).

1H NMR (300 MHz, Methanol-d4) δ 2.17 (d, J = 7.1 Hz, 2H), 1.18 (dddd, J = 11.1, 8.0,

3.7, 1.7 Hz, 4H), 1.13 – 0.99 (m, 2H), 0.83 – 0.55 (m, 3H), 0.49 – 0.28 (m, 2H). 13C NMR (75 MHz, MeOD) δ 46.4 (–), 37.2 (+), 31.3 (–), 27.1 (–), 26.6 (–).

Hexadecan-1-amine hydrochloride.

Hydrogenation of hexadecanenitrile (125 mg, 0.5 mmol) according to the procedure D


(137 mg, 98%).


1.20 (br. s, 28H), 1.03 – 0.71 (m, 3H). 13C NMR (75 MHz, MeOD) δ 40.8 (+), 33.1 (+), 30.84 (+),30.8 (+), 30.7 (+), 30.6 (+),

30.5 (+), 30.3 (+), 28.6 (+), 27.5 (+), 23.8 (+), 14.5 (–).

Heptylamine hydrochloride. Hydrogenation of 3-phenylpropanenitrile (65 µL, 0.5 mmol) according to the procedure

D and subsequent treatment with HCl in ether afforded the title compound as a white

solid (83 mg, 97%).

1H NMR (300 MHz, Methanol-d4) 7.28 – 6.73 (m, 5H), 2.85 – 2.63 (m, 2H), 2.60 – 2.41

(m, 2H), 1.79 (tt, J = 9.4, 6.8 Hz, 2H). 13C NMR (75 MHz, MeOD) δ 141.8, 129.5 (+), 129.4 (+), 127.3(+), 40.3 (–), 33.5 (–),

30.3 (–).

Cyclopropylmethanamine hydrochloride.

Hydrogenation of cyclopropanenitrile (37 µL, 0.5 mmol) according to the procedure D


(49 mg, 91%).

1H NMR (300 MHz, Methanol-d4) δ 2.81 (d, J = 7.5 Hz, 2H), 1.10 (tt, J = 7.8, 4.8 Hz,

1H), 0.80 – 0.58 (m, 2H), 0.50 – 0.21 (m, 2H). 13C NMR (75 MHz, MeOD) δ 45.7 (–), 9.5 (+), 4.4 (–).

Cyclopentylmethanamine hydrochloride.

Hydrogenation of cyclopentanenitrile (52 µL, 0.5 mmol) according to the procedure D


(56 mg, 83%).

1H NMR (300 MHz, Methanol-d4) δ 2.89 (d, J = 7.5 Hz, 2H), 2.17 (dt, J = 15.6, 7.8 Hz,

1H), 1.96 – 1.81 (m, 2H), 1.78 – 1.54 (m, 4H), 1.35 – 1.05 (m, 2H). 13C NMR (75 MHz, MeOD) δ 45.5 (–), 39.3 (+), 31.2 (–), 26.0 (–).

2-(4-Methoxyphenyl)ethan-1-aminehydrochloride. Hydrogenation of 2-(4-methoxyphenyl)acetonitrile (67 µL, 0.5 mmol) according to the

procedure D and subsequent treatment with HCl in ether afforded the title compound as a

white solid (90 mg, 96%).

1H NMR (300 MHz, Methanol-d4) δ 7.33 – 7.09 (m, 2H), 6.94 – 6.80 (m, 2H), 3.76 (s,

3H), 3.13 (dd, J = 9.1, 6.5 Hz, 2H), 2.91 (dd, J = 8.9, 6.6 Hz, 2H). 13C NMR (75 MHz, MeOD) δ 160.3, 130.8 (+), 129.7, 115.3 (+), 55.7 (+), 42.2 (–), 33.7

(–).

Decan-1-amine hydrochloride.

Hydrogenation of decanenitrile (94 µL, 0.5 mmol) according to the procedure D and


mg, 99%).

1H NMR (300 MHz, Methanol-d4) δ 2.97 (t, J = 7.7 Hz, 2H), 1.80 – 1.62 (m, 2H), 1.54 –

1.18 (m, 14H), 1.12 – 0.69 (m, 3H). 13C NMR (75 MHz, MeOD) δ 40.8 (+), 33.0 (+), 30.6 (+), 30.5 (+), 30.4 (+), 30.2 (+),

28.5 (+), 27.5 (+), 23.7 (+), 14.4 (–).

Octadecan-1-amine hydrochloride. Hydrogenation of stearonitrile (140 mg, 0.5 mmol) according to the procedure D and


mg, 72%).

1H NMR (300 MHz, Methanol-d4) δ 2.91 (t, J = 7.7 Hz, 2H), 1.77 – 1.56 (m, 2H), 1.29

(s, 32H), 1.01 – 0.84 (m, 3H). 13C NMR (75 MHz, MeOD) δ 40.8 (+), 33.1 (+), 30.8 (+), 30.8 (+), 30.7 (+), 30.5 (+),

30.5 (+), 30.3 (+), 28.6 (+), 27.5 (+), 23.8 (+), 14.5 (–).

Propylamine hydrochloride.

Hydrogenation of propanenitrile (35 µL, 0.5 mmol) according to the procedure D and


mg, 84%).

1H NMR (300 MHz, Methanol-d4) δ 3.01 – 2.77 (m, 2H), 1.85 – 1.55 (m, 2H), 1.01 (t, J

= 7.5 Hz, 3H). 13C NMR (75 MHz, MeOD) δ 42.4 (+), 21.9 (+), 11.2 (–).

Adamantan-1-ylmethanamine hydrochloride. white solid 89 mg, 88%

Hydrogenation of adamantanenitrile (80 mg, 0.5 mmol) according to the procedure D at

150°C and subsequent treatment with HCl in ether afforded the title compound as a white

solid (89 mg, 88%).

1H NMR (300 MHz, Methanol-d4) δ 2.63 (s, 2H), 2.03 (br. s, 3H), 1.76 (m, 6H), 1.61

(m, 6H). 13C NMR (75 MHz, MeOD) δ 52.0 (+), 40.4 (+), 37.5 (+), 33.0, 29.4 (–).

Heptylamine hydrochloride. Hydrogenation of cinnamonitrile (63 µL, 0.5 mmol) according to the procedure D and


mg, 85%).

1H NMR (300 MHz, Methanol-d4) 7.28 – 6.73 (m, 5H), 2.85 – 2.63 (m, 2H), 2.60 – 2.41

(m, 2H), 1.79 (tt, J = 9.4, 6.8 Hz, 2H). 13C NMR (75 MHz, MeOD) δ 141.8, 129.5 (+), 129.4 (+), 127.3(+), 40.3 (–), 33.5 (–),

30.3 (–).

2,3-Diphen0ylpropan-1-amine.

Hydrogenation of (Z)-2,3-diphenylacrylonitrile (103 mg, 0.5 mmol) according to the

procedure D afforded the title compound as a yellow oil (95 mg, 90%).

1H NMR (300 MHz, CDCl3) δ 7.86 – 6.47 (m, 10H), 3.47 – 2.13 (m, 5H), 1.10 (br. s,

2H). 13C NMR (75 MHz, CDCl3) δ 143.0, 140.3, 129.1 (+), 128.5 (+), 128.2 (+), 128.0 (+),

126.5 (+), 125.9 (+), 51.6 (+), 47.1 (–), 40.8 (–).

Methyl stearate.

Hydrogenation of methyl oleate (169 µL, 0.5 mmol) according to the procedure F at 60°C


1H NMR (300 MHz, CDCl3) δ 3.66 (s, 3H), 2.29 (t, J = 7.5 Hz, 2H), 1.75 – 1.51 (m, 2H),

1.25 (s, 28H), 0.95 – 0.78 (m, 3H). 13C NMR (75 MHz, CDCl3) δ 174.4, 51.5 (–), 34.3 (+), 32.1 (+), 29.8 (+), 29.8 (+), 29.8

(+), 29.8 (+), 29.7 (+), 29.6 (+), 29.5 (+), 29.4 (+), 29.3 (+), 25.1 (+), 22.8 (+), 14.2 (–).


Hydrogenation of cinnamyl alcohol (67 mg, 0.5 mmol) according to the procedure F


1H NMR (300 MHz, Chloroform-d) δ 7.37 – 7.27 (m, 2H), 7.25 – 7.17 (m, 3H), 3.68 (t, J

= 6.5 Hz, 2H), 2.78 – 2.67 (m, 2H), 1.99 – 1.84 (m, 2H), 1.79 (br. s, 1H).

δ 7.47 – 7.24 (m, 5H), 4.62 (dd, J = 7.0, 6.2 Hz, 1H), 2.22 (br. s, 1H), 1.99 – 1.64 (m,

2H), 0.97 (t, J = 7.4 Hz, 3H). 13C NMR (75 MHz, CDCl3) δ 141.9, 128.5 (+), 128.5 (+), 125.9(+), 62.3 (–), 34.3 (–),

32.2 (–).

1-Methoxy-4-propylbenzene

Hydrogenation of 1-allyl-4-methoxybenzene (148 mg, 1.0 mmol) according to the

procedure F afforded the title compound as a colorless oil (108 mg, 72%).

1H NMR (300 MHz, CDCl3) δ 7.14 (dt, J = 8.8, 0.6 Hz, 2H), 6.95 – 6.78 (m, 2H), 3.83 (s,

3H), 2.69 – 2.40 (m, 2H), 1.84 – 1.53 (m, 2H), 0.99 (t, J = 7.3 Hz, 3H). 13C NMR (75 MHz, CDCl3) δ 157.8, 134.9, 129.4 (+), 113.8 (+), 55.3 (+), 37.3 (–), 24.9

(–), 13.9 (+).

7,8-Dihydro-α-ionone

Hydrogenation of α-ionone (103 µL, 0.5 mmol) according to the procedure F afforded the

title compound as a colorless oil (93 mg, 96%).

1H NMR (300 MHz, CDCl3) δ 5.33 (ddt, J = 4.7, 3.4, 1.7 Hz, 1H), 2.54 – 2.38 (m, 2H),

2.13 (t, J = 0.5 Hz, 3H), 2.02 – 1.90 (m, 2H), 1.85 – 1.68 (m, 1H), 1.66 (qd, J = 2.0, 0.5

Hz, 3H), 1.65 – 1.52 (m, 2H), 1.51 – 1.43 (m, 1H), 1.44 – 1.33 (m, 1H), 1.23 – 1.06 (m,

1H), 0.91 (s, 3H), 0.87 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 209.3, 135.7, 121.2 (+), 48.6 (+), 43.9 (–), 32.7, 31.7 (–),

30.1 (+), 27.8 (+), 27.7 (+), 24.5 (–), 23.7 (+), 23.1 (–).

Methyl 2-hydroxy-3-methoxy-5-propylbenzoate

Hydrogenation of methyl 5-allyl-3-methoxysalicylate (111 mg, 0.5 mmol) according to

the procedure F afforded the title compound as a colorless oil (105 mg, 94%).

1H NMR (300 MHz, CDCl3) δ 10.79 (s, 1H), 7.22 (d, J = 1.9 Hz, 1H), 6.85 (d, J = 2.0 Hz,

1H), 3.92 (s, 3H), 3.87 (s, 3H), 2.67 – 2.32 (m, 2H), 1.60 (dq, J = 14.7, 7.3 Hz, 2H), 0.92

(t, J = 7.3 Hz, 3H). 13C NMR (75 MHz, CDCl3) δ 171.0, 150.2, 148.3, 133.0, 120.1 (+), 117.4 (+), 112.1,

56.3 (+), 52.3 (+), 37.6 (–), 24.6 (–), 13.8 (+).

2-Methyl-1,2,3,4-tetrahydroquinoline.

Hydrogenation of quinaldine (67 µL, 0.5 mmol) according to the procedure G afforded

the title compound as a yellow oil (66 mg, 90%).

1H NMR (300 MHz, Chloroform-d) δ 7.09 – 6.91 (m, 2H), 6.65 (td, J = 7.4, 1.2 Hz, 1H),

6.51 (dd, J = 8.3, 1.2 Hz, 1H), 3.71 (br. s, 1H), 3.43 (dqd, J = 10.0, 6.3, 2.8 Hz, 1H), 3.06

– 2.58 (m, 2H), 1.97 (dddd, J = 12.9, 5.7, 3.5, 2.9 Hz, 1H), 1.63 (dddd, J = 12.8, 11.4, 9.9,

5.5 Hz, 1H), 1.25 (d, J = 6.3 Hz, 3H). 13C NMR (75 MHz, Chloroform-d) δ 144.7, 129.2 (+), 126.6 (+), 121.0, 116.9 (+), 113.9

(+), 47.1 (+), 30.1 (–), 26.6 (–), 22.6 (+).

1,2,3,4-Tetrahydroquinoline.

Hydrogenation of quinoline (59 µL, 0.5 mmol) according to the procedure G afforded the

title compound as a colorless oil (58 mg, 87%).

1H NMR (300 MHz, Chloroform-d) δ 7.07 – 6.88 (m, 2H), 6.64 (td, J = 7.4, 1.2 Hz, 1H),

6.55 – 6.35 (m, 1H), 3.85 (br. s, 1H), 3.52 – 3.16 (m, 2H), 2.80 (t, J = 6.4 Hz, 2H), 2.21 –

1.68 (m, 2H). 13C NMR (75 MHz, Chloroform-d) δ 144.9, 129.6 (+), 126.8 (+), 121.5 , 117.0 (+),

114.3 (+), 42.1 (–), 27.1 (–), 22.3 (–).

2-Phenyl-1,2,3,4-tetrahydroquinoline.

Hydrogenation of 2-phenylquinoline (102 µL, 0.5 mmol) according to the procedure G


1H NMR (300 MHz, Chloroform-d) δ 7.54 – 7.30 (m, 5H), 7.08 (ddt, J = 8.1, 7.4, 0.8 Hz,

2H), 6.72 (td, J = 7.4, 1.2 Hz, 1H), 6.59 (dd, J = 8.5, 1.3 Hz, 1H), 4.49 (dd, J = 9.2, 3.4

Hz, 1H), 4.08 (br. s, 1H), 3.05 – 2.91 (m, 1H), 2.79 (dt, J = 16.4, 4.8 Hz, 1H), 2.18 (dddd,

J = 13.3, 5.5, 4.5, 3.4 Hz, 1H), 2.05 (dddd, J = 12.9, 10.5, 9.2, 5.1 Hz, 1H). 13C NMR (75 MHz, Chloroform-d) δ 144.9, 144.8, 129.4 (+), 128.6 (+), 127.5 (+), 127.0

(+), 126.6 (+), 120.9, 117.2 (+), 114.1 (+), 56.3 (+), 31.1 (–), 26.5 (–).

1,2,3,4-Tetrahydro-1,5-naphthyridine.

Hydrogenation of 1,5-naphthyridine (65 mg, 0.5 mmol) according to the procedure G


1H NMR (300 MHz, Chloroform-d) δ 7.81 (dd, J = 4.7, 1.5 Hz, 1H), 6.83 (ddt, J = 8.0,

4.7, 0.7 Hz, 1H), 6.67 (dd, J = 8.0, 1.5 Hz, 1H), 3.95 (br s, 1H), 3.31 – 3.19 (m, 2H), 2.89

(t, J = 6.5 Hz, 2H), 2.08 – 1.91 (m, 2H). 13C NMR (75 MHz, Chloroform-d) δ 142.7, 141.0, 137.8 (+), 121.9 (+), 120.2 (+), 41.5

(–), 30.4 (–), 21.8 (–).

8-Methyl-1,2,3,4-tetrahydroquinoline

Hydrogenation of 8-methylquinoline (66 µL, 0.5 mmol) according to the procedure G


1H NMR (300 MHz, Chloroform-d) δ 6.97 – 6.80 (m, 2H), 6.60 (t, J = 7.4 Hz, 1H), 3.58

(br. s, 1H), 3.49 – 3.35 (m, 2H), 2.84 (t, J = 6.4 Hz, 2H), 2.12 (s, 3H), 2.08 – 1.86 (m,

2H). 13C NMR (75 MHz, Chloroform-d) δ 142.8, 127.9 (+), 127.5 (+), 121.3, 120.9, 116.5

(+), 42.4 (–), 27.4 (–), 22.3 (–), 17.3 (+).

5-Fluoro-8-methoxy-1,2,3,4-tetrahydroquinoline.

Hydrogenation of 5-fluoro-8-methoxy-quinoline (88.5 mg, 0.5 mmol) according to the

procedure G afforded the title compound as a colorless oil (89 mg, 98%).

1H NMR (300 MHz, Chloroform-d) δ 6.52 (dd, J = 8.8, 4.9 Hz, 1H), 6.28 (t, J = 9.0 Hz,

1H), 4.36 (br. s, 1H), 3.81 (s, 3H), 3.32 (td, J = 5.9, 2.2 Hz, 2H), 2.75 (dd, J = 7.0, 6.0 Hz,

2H), 2.15 – 1.66 (m, 2H). 13C NMR (75 MHz, Chloroform-d) δ 156.0 (d, J = 234.3 Hz), 142.2 (d, J = 1.7 Hz),

135.8 (d, J = 8.7 Hz), 108.8 (d, J = 23.5 Hz), 107.2 (d, J = 10.3 Hz) (+), 100.4 (d, J = 23.9

Hz) (+), 55.8 (+), 40.9 (–), 21.2(–), 19.9 (d, J = 3.8 Hz) (–).

section S10. Procedures for dehydrogenation reactions (figs. S17 to S19)

Figure S17 depicts the setup of activity measurements with the manual burettes.

fig. S17. Manual burette setup.

Procedure for the dehydrogenation of 1,2,3,4-tetrahydroquinaldine:

A 25 mL Schlenk tube was charged at ambient atmosphere with Ni-Phen@SiO2-1000

catalyst (500 mg, 20 mol% Ni), 1,2,3,4-tetrahydroquinaldine (180 µL, 1.25 mmol, 1.0

equiv.). The Schlenk tube was connected to the reaction setup and the whole system was

flushed with argon for approximately 20-30 minutes (fig. S17), followed by the heating

to 200°C in aluminum block. The desired temperature was achieved within 20 min. The

measurement of the gas evolution was started together with starting the heating. The

influence of temperature on the volume was corrected by performing reactions without a

catalyst (See calculation of conversion). After running the reaction for the desired time, a

gas sample was taken to determine the identity and quantity of the gas components. The

reaction was performed four times, the standard deviation divided by the average value *

100% is in between 1 and 10 %.

Gas evolution curves

Figure S18 provides original data as measured for the hydrogen evolution from the

substrate. The volumes are not corrected by blank volume.

0 5 10 15 20 25

10

20

30

40

50

60

Experiment 1

Experiment 2

Experiment 3

Experiment 4

Blank volume

Ga

s e

volu

tio

n,

ml

time, h

fig. S18. Gas evolution from 1,2,3,4-tetrahydroquinaldine. Reaction conditions: 180

µL substrate, 5 ml triglyme, 0.5 g Ni-Phen@SiO2-1000, 200°C (experiments 1-4).

Gas evolution curves demonstrate that the majority of hydrogen evolves within the first

10 hours, after which evolution slows down, eventually reaching a plateau. The blank

volume curve shows an initial increase of 14 mL and then remains stable.

GC analysis

An example of the resulting GC is shown below (fig. S19). FID signal (retention time

28.39 min) in the upper part shows the substrate (1,2,3,4-tetrahydroquinaldine), which is

in the vapor phase. The contribution of this compound to the overall volume is equalized

by correction with the blank volume.

The TCD signals clearly demonstrate a good selectivity towards hydrogen, while only

small amounts (113, 121 and 818 ppm, respectively) of CO, CH4 and CO2 were formed.

These gases are in a mixture with Ar which is not detected as Ar is also used as carrier

gas.

GC analysis provides directly the volume percentage of the different components of the

collected gases. H2, CO2, CO, and CH4.

fig. S19. Gas composition analysis by GC.

Calculation of conversion

The measured gas volumes were corrected by a blank volume (gas evolution measured in

a reaction performed without catalyst under the same conditions).

The gas production was calculated by the equation (S1):

Gas production = 𝑉𝑜𝑏𝑠 − 𝑉𝑏𝑙𝑎𝑛𝑘 (𝑺𝟏)

where Vobs and Vblank are the gas volume measured in the catalytic reaction and the blank

reaction, respectively. Conversion was calculated by the equation (S2):

Conversion = 𝑉𝑜𝑏𝑠 − 𝑉𝑏𝑙𝑎𝑛𝑘

𝑉𝑚,𝐻2,25°𝐶 ∗ 𝑛𝐻2𝑒𝑥𝑝𝑒𝑐𝑡𝑒𝑑

(𝑺𝟐)

The calculation of 𝑉𝑚,𝐻2,25°𝐶 was carried out using Van der Waals equation (S3):

𝑉𝑚,𝐻2,25°𝐶 =𝑅𝑇

𝑝+ 𝑏 −

𝑎

𝑅𝑇= 24.48

𝐿

𝑚𝑜𝑙 (𝑺𝟑)

Where:

R: 8.3145 m³·Pa·mol-1·K-1;

T: 298.15 K;

P: 101325 Pa;

a: 24.7·10-3·Pa·m6·mol-2;

b: 26.6·10-6 m³·mol-1

Based on evolved hydrogen a conversion of 74% was calculated after 24h (note: 100%

yield corresponds to 61 mL of H2 gas), which corresponds with conversion calculated

based on quantification of dehydrogenated substrate measured via GC of the liquid phase

(78%).

Hot filtration test.

To confirm the heterogeneous character of the catalyst, a hot filtration test was

performed. A reaction was set according to the dehydrogenation procedure described

above. After 4 h at 200°C the reaction mixture was gradually cooled to 100°C while

stirring in the heating block (~ 1h). A sample of the hot reaction mixture was quickly

filtered through a short Celite plug (~2 cm) preheated with a heat gun to 120°C. The

resulting mixture was analyzed by GC, giving 35.1% conversion. This mixture was place

back in new Schlenk tube and heated to 200°C under argon for additional 16h. Analysis

of the resulting reaction mixture showed 36.0% conversion. Moreover in the liquid phase

only trace amounts of nickel was observed (0.06 ppm)

Procedure for the oxidation of 1,2,3,4-tetrahydroquinoline with air:

An 8 mL glass vial (Ø – 14 mm, height 50 mm) equipped with a Teflon-coated oval

magnetic stirring bar (8 × 5 mm) and a plastic screw cap was charged with 1,2,3,4-

tetrahydroquinoline (63 µl, 0.5 mmol, 1.0 equiv.), 40 mg of nickel-based catalyst (~4

mol% Ni), 1 mL of deionized water and 1 mL of methanol. The silicone septa was

punctured with a 26 gauge syringe needle (0.45 × 12 mm) and the vial was placed in the

aluminum plate which was then transferred into the 300 mL autoclave. Once sealed, the

autoclave was placed into an aluminum block and purged 3 times with air (at 5-10 bar).

Then it was pressurized to 10 bar air, heated up and kept at 100°C under thorough stirring

(700 rpm). After 20 h, the autoclave was removed from the aluminum block and cooled

to room temperature in a water bath. The remaining air was discharged and the vail

containing reaction mixture was removed from the autoclave. To the crude reaction

mixture 100 µL of n-hexadecane (internal standard) was added, followed by the addition

of 6 mL of ethyl acetate. The resulting mixture was intensively stirred for 30 seconds and

then the solid catalyst was separated by centrifugation and the liquid phase was subjected

to GC analysis.

section S11. Catalyst recycling

Hydrogenation of nitroarenes (Procedure A).

Hydrogenation of nitrobenzene: Four 8 mL glass vials (Ø – 14 mm, height 50 mm)

equipped with a Teflon-coated oval magnetic stirring bar (8 × 5 mm) and a plastic screw

cap were charged with nitrobenzene (51 µl, 0.5 mmol, 1.0 equiv.), 40 mg of nickel-based

catalyst (~4 mol% Ni), 1 mL of deionized water and 1 mL of methanol. The silicone

septa was punctured with a 26 gauge syringe needle (0.45 × 12 mm) and the vial was

placed in the aluminum plate which was then transferred into the 300 mL autoclave.

Once sealed, the autoclave was placed into an aluminum block and purged 3 times with

hydrogen (at 5-10 bar). Then it was pressurized to 10 bar, heated up and kept at 40°C

under thorough stirring (700 rpm). After 16 h, the autoclave was removed from the

aluminum block and cooled to room temperature in a water bath. The remaining

hydrogen was discharged and the vails containing reaction products were removed from

the autoclave. One reaction was used to determine the amount of leached Ni. The solid

catalyst was settled by centrifugation and the liquid phase was filtered through a short

Celite plug, which was then subjected to AAS analysis. Three reaction vials were diluted

with 6 mL of ethyl acetate and 100 µL of n-hexadecane were added. The resulting

mixture was intensively stirred for 30 seconds and then the solid catalyst was separated

by centrifugation and the liquid phase was subjected to GC analysis. GC conversions

reported are the average of three runs. The solid catalyst was washed with 6 mL of ethyl

acetate (x2) and 6 mL of acetone (x2) and then dried under vacuum for 4 h used for the

next run.

table S5. Recycling experiments.

1 2 3 4 5 6 7

0

10

20

30

40

50

60

70

80

90

100

Reaction run

Conversion, %

Yield, %

table S6. Nickel leaching in the recycling experiments.

Run / Ni

(ppm) 1 2 3 4 5 6 7

Probe A 0.016 0.016 0.016 0.050 0.006 0.009 0.020

Probe B 0.017 0.008 0.012 0.008 0.003 0.001 0.011

table S7. Effect of the pH on hydrogenation of nitrobenzene.

3 5 7 9 11

0

10

20

30

40

50

60

Conversion, %

Yield, %

pH

section S12. Nuclear magnetic resonance (NMR) spectral charts

supplementary materials for · effect of the ph on hydrogenation of nitrobenzene. section s1....

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