10.1002/ejic.202000068
European Journal of Inorganic Chemistry
10878). All NMR data, in the manuscript and in the ESI ex-
perimental, are expressed as chemical shift in parts per mil-
lion (ppm) relative to the residual solvent used as an inter-
nal standard for the δ scale. The multiplicity of each signal
is designed as follow; s (singlet), d (doublet), t (triplet), b
(broad), m (multiplet). Infrared spectrometry was carried
out with a Bruker-ALPHA FT-IR spectrometer with a spec-
tral range of 7500 to 375 cm-1 (wavelength range: 1.3 to 27
mm). The solids were analyzed by ATR - Attenuated Total
Reflectance - sampling method and the spectrums are ex-
ploited on OMNIC 7.3 or Origins 8.6. Gas chromatography
was used to analyze the content of the gas phase with a CO
quantification limit of 10 ppm. The samples were analyzed
on Agilent Technologies 6890N GC system (HP Plot Q / FID
– hydrocarbons, Carboxen / TCD - permanent gases, He car-
rier gas.). X-ray structure analyses were carried out on
Bruker Kappa APEX II Duo diffractometer. Synthesis of (6-
equilibrate under argon for 60 minutes. The catalyst was
added in a mini-Teflon cup and the gas evolution was mon-
itored.
ASSOCIATED CONTENT
Supporting Information
General methods, equipment, procedures, calculation of TON
and TOF, gas evolution plots, analytical data, ligand synthesis,
crystallographic data for the intermediate [Ru(κ3-
CNN)(dppb)(OOCH)].
AUTHOR INFORMATION
Corresponding Author
* Matthias Beller, e-mail: matthias.beller@catalysis.de
(p-tolyl)pyridin-2-yl)methanamine
4, complexes
[RuCl2(PPh3)(dppb)] 5, [Ru(κ3-CNN)(dppb)Cl] 6, [Ru(κ3-
CNN)(dppb)(OOCH)] 8, [cis-Ru(AMP)(PPh3)2Cl], [trans-
Ru(AMP)(PPh3)2Cl] 9, [Ru(AMP)(dppb)Cl] 10, [RuCl2CO2]n,
[Ru(AMP)(CO)2Cl] 11, [Ru(κ2-CNN)(CO)2Cl] 12, [Ru(κ3-
CNN)(CO)2Cl] 13, [Ru(bpy)(PPh3)2Cl] and the unsuccessful
attempt of [Ru(κ3-CNN)(bpy)Cl] were all done according to
reported literature and their synthesis are reported in the
supporting information provided along with analytical data.
ACKNOWLEDGMENT
We thank all members of the research group “catalysis for en-
ergy” (LIKAT), Maximilian Marx, Dr. Pavel Ryabchuk and Elis-
abetta Alberico for scientific discussion and valuable sugges-
tions. We thank PD Dr. W. Baumann and Dr. A. Spannenberg for
their technical and analytical support (all from LIKAT).
ABBREVIATIONS
Formic Acid (FA), Dehydrogenation (DH), Gas Chromatography
(GC), Turnover Number (TON), Turnover Number Frequency
(TOF), Nuclear Magnetic Resonance (NMR), Transfer Hydro-
genation (TH), Dimethyloctylamine (DMOA), AMP (4-(ami-
nomethyl)pyridine), Dichloromethane (DCM).
Typical procedure for the formic acid dehydrogenation:
A double wall reactor was equipped with a double burette
manual set-up. The set up was evacuated and potassium hy-
droxide (KOH), water (H2O), triglyme (MeO[CH2O]3Me) and
formic acid (HCOOH) were successively added. The reaction
mixture was heated to the desired temperature was left to
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