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Supplementary Information Supplementary Figures Supplementary Fig. 1 Methanol-derived protons in methanediol in the formaldehyde production from methanol: The water formed in the oxidation is used to form methanediol.

Supplementary Fig. 2 Initial period of the dehydrogenation of methanediol (37 wt.% aq. formaldehyde) under base free conditions: Time-resolved gas volumes with various catalyst loadings of [RuCl 2 (p-cymene)] 2 1 at 95 C.

Supplementary Fig. 3 MS-monitoring of the H 2 and subsequent CO 2 evolution: The H 2 /CO 2 -ratios indicate a twostep dehydrogenation process of methanediol via formic acid to hydrogen and carbon dioxide.

Supplementary Fig. 4 MS-monitoring of the H 2 and 13 CO 2 evolution showing no formation of 13 CO: a) Bar-mode scan, b) Time-resolved plot of the selected species.

Supplementary Fig. 5 Full spectrogram of Fig. 3: Note the MS has sensitivity down to partial pressures of 10-10 torr (Spectrometer specific unit is torr not MPa).

Supplementary Fig. 6 Assignment of carbon atoms in µ-chlorido,-µ-formiato,-µ-hydrido(p-cymene)ruthenium(ii) dimer tetrafluoroborate salt 3-BF 4 : As the numbering indicates, the molecule has a symmetry plane through the bridging ligands. Refer to Supplementary Table 3 for chemical shifts.

Supplementary Fig. 7 Graphical assignment of 3-BF 4 : The correlations are extracted from H,H-COSY-, H,C-HMBC, H,H-NOESY- und F,H-HOESY-data (refer Supplementary Table 3).

Supplementary Fig. 8 1 H NMR spectrum of 3: Spectrum of the reaction solution used for the identification of 3 (500 MHz, water suppression with excitation sculpting, 298 K). A D 2 O-insert was used as lock to prevent exchange processes.

Supplementary Fig. 9 13 C{ 1 H} NMR spectrum of 3: Proton-decoupled 13 C NMR spectrum of the reaction solution used for the identification of 3 (125 MHz, solution in D 2 O, 298 K).

Supplementary Fig. 10 Gradient-selected H-H COSY NMR spectrum of 3: H-H COSY NMR spectrum of the reaction solution used for the identification of 3 (600 MHz, solution in D 2 O, 298 K).

Supplementary Fig. 11 Gradient-selected H-H NOESY NMR spectrum of 3: H-H NOESY NMR spectrum of the reaction solution used for the identification of 3 (500 MHz, mixing time 800 ms, water suppression with excitation sculpting, solution in H 2 O with D 2 O insert, 298 K).

Supplementary Fig. 12 Gradient-selected H-C HMQC NMR spectrum of 3: H-C HMQC NMR spectrum of the reaction solution used for the identification of 3 (600/150 MHz, solution in D 2 O, 298 K).

Supplementary Fig. 13 Gradient-selected H-C HMBC NMR spectrum of 3: H-C HMBC NMR spectrum of the reaction solution used for the identification of 3 (500/125 MHz, solution in H 2 O with D 2 O insert, 298 K). Hydride resonance correlations are marked with red boxes.

Supplementary Fig. 14 1 H NMR of complex [(Ru(p-cymene)) 2 μ-h(µ-hco 2 )μ-cl] + [BF 4 ] - 3-BF 4 isolated during dehydrogenation of paraformaldehyde in water: 1 H NMR spectrum of 3-BF 4 direct after isolation (300 MHz, CD 2 Cl 2, 298 K, Methods protocol 4).

Supplementary Fig. 15 13 C NMR of complex [(Ru(p-cymene)) 2 μ-h(µ-hco 2 )μ-cl] + [BF 4 ] - 3-BF 4 isolated during dehydrogenation of paraformaldehyde in water: 13 C NMR spectrum of 3-BF 4 direct after isolation (75 MHz, CD 2 Cl 2, 298 K, Methods protocol 4).

Supplementary Fig. 16 1 H NMR of complex [(Ru(p-cymene)) 2 μ-h(µ-hco 2 )μ-cl] + [BF 4 ] - 3-BF 4 isolated during dehydrogenation of paraformaldehyde in water: 1 H NMR spectrum of 3-BF 4 after standing over night (400 MHz, CD 2 Cl 2, 298 K, Methods protocol 4).

Supplementary Fig. 17 19 F NMR of complex [(Ru(p-cymene)) 2 μ-h(µ-hco 2 )μ-cl] + [BF 4 ] - 3-BF 4 isolated during dehydrogenation of paraformaldehyde in water: 19 F NMR spectrum of 3-BF 4 after standing over night (376 MHz, CD 2 Cl 2, 298 K, Methods protocol 4).

Supplementary Fig. 18 1 H NMR of complex [(Ru(p-cymene)) 2 μ-h(µ-hco 2 )μ-cl] + [BF 4 ] - 3-BF 4 synthesised using formic acid: 1 H NMR spectrum of 3-BF 4 after standing over night (400 MHz, CD 2 Cl 2, 298 K, Methods protocol 5).

Supplementary Fig. 19 13 C{ 1 H} NMR of complex [(Ru(p-cymene)) 2 μ-h(µ-hco 2 )μ-cl] + [BF 4 ] - 3-BF 4 synthesised using formic acid: Proton-decoupled 13 C NMR spectrum of 3-BF 4 after standing over night (100 MHz, CD 2 Cl 2, 298 K, Methods protocol 5).

Supplementary Fig. 20 19 F NMR of complex [(Ru(p-cymene)) 2 μ-h(µ-hco 2 )μ-cl] + [BF 4 ] - 3-BF 4 synthesised using formic acid: 19 F NMR spectrum of 3-BF 4 after standing over night (376 MHz, CD 2 Cl 2, 298 K, Methods protocol 5).

Supplementary Fig. 21 H-C HMBC NMR of complex [(Ru(p-cymene)) 2 μ-h(µ-hco 2 )μ-cl] + [BF 4 ] - 3-BF 4 synthesised using formic acid: H-C HMBC NMR spectrum of 3- BF 4 after standing over night (400/100 MHz, CD 2 Cl 2, 298 K, Methods protocol 5).

Supplementary Fig. 22 H-C HMQC NMR of complex [(Ru(p-cymene)) 2 μ-h(µ-hco 2 )μ-cl] + [BF 4 ] - 3-BF 4 synthesised using formic acid: H-C HMQC NMR spectrum of 3- BF 4 after standing over night (400/100 MHz, CD 2 Cl 2, 298 K, Methods protocol 5).

Supplementary Fig. 23 H-H NOESY NMR of complex [(Ru(p-cymene)) 2 μ-h(µ-hco 2 )μ-cl] + [BF 4 ] - 3-BF 4 synthesised using formic acid: H-H NOESY NMR spectrum of 3- BF 4 after standing over night (400 MHz, 850 ms mixing time, CD 2 Cl 2, 298 K, Methods protocol 5).

Supplementary Fig. 24 H-F HOESY NMR of complex [(Ru(p-cymene)) 2 μ-h(µ-hco 2 )μ-cl] + [BF 4 ] - 3-BF 4 synthesised using formic acid: H-F HOESY NMR spectrum of 3- BF 4 after standing over night and (400/376 MHz, 700 ms mixing time, CD 2 Cl 2, 298 K, Methods protocol 5).

Supplementary Fig. 25 Overview of the reaction pathways for the formation of ruthenium dimer 3 depending on the ph: Best results in the range of ph 3-9 with maximum around ph 5.5 in terms of catalytic activity. Selected species assigned by NMR and ESI-MS; for ph-depended hydrolysis products also see Supplementary Ref. 1, ESI-MS for 3 see Fig. 4.

Supplementary Fig. 26 Exemplary ESI-MS spectrogram of a reaction solution: With 3 (553 m/z). The other species are related to hydrolysis products (504 m/z, 488 m/z, 287 m/z) of 1 (577 m/z) and the most intensive signals (504 m/z and 465 m/z) might be also formed under MS conditions. 1

Supplementary Fig. 27 HR-ESI-MS spectrogram of [(Ru(p-cymene)) 2 μ-h(µ-hco 2 )μ-cl] + [BF 4 ] - 3-BF 4 : HRMS (m/z): [M-BF 4 ] + calcd. for C 21 ClH 30 O 2 Ru 2, 553.0016; found, 553.0018.

Supplementary Fig. 28 Set up for dehydrogenation reactions: The set up allows both quantification and qualitative analysis at the same time.

Supplementary Tables Supplementary Table 1: Overview of isotope-labelling MS-experiments with 1 H, 2 H, 13 C and 18 O isotopes. Entry H 2 C(OH) 2 -Source Water Assigned Products a Selected Ru-Species b 1 aq. CH 2 O (FA) H 2 O H 2 ; CO 2 [(Ru(p-cymene)) 2 µ-h(hco 2 )µ-cl] + 3 2 aq. CD 2 O D 2 O D 2 ; CO 2 [(Ru(p-cymene)) 2 µ-d(dco 2 )µ-cl] + 4 3 HO(CH 2 O) n H H 2 O H 2 ; CO 2 [(Ru(p-cymene)) 2 µ-h(hco 2 )µ-cl] + 3 4 HO(CH 2 O) n H D 2 O D 2 > HD > H 2 ; CO 2 [(Ru(p-cymene)) 2 µ-h(dco 2 )µ-cl] + 5 5 HO(CH 2 O) n H HDO c D 2 ~ HD ~ H 2 ; CO 2 n. a. 6 d HO(CH 2 O) n H H 2 18 O H 2 ; 18 O 2 ~ C 18 O 2 >> C( 18 O 16 O) ~ C 16 O 2 [(Ru(p-cymene)) 2 µ-h(hc 18 O 2 )µ-cl] + 6 7 DO(CD 2 O) n D D 2 O D 2 ; CO 2 [(Ru(p-cymene)) 2 µ-d(dco 2 )µ-cl] + 4 8 DO(CD 2 O) n D HDO c D 2 ~ HD ~ H 2 ; CO 2 n. a. 9 DO(CD 2 O) n D H 2 O H 2 > HD >> D 2 ; CO 2 ; D 2 O e [(Ru(p-cymene)) 2 µ-h(dco 2 )µ-cl] + 5 10 HO( 13 CH 2 O) n H H 2 O H 2 ; 13 CO 2 [(Ru(p-cymene)) 2 µ-h(h 13 CO 2 )µ-cl] + 7 11 HO( 13 CH 2 O) n H HDO c D 2 ~ HD ~ H 2 ; 13 CO 2 n. a. 12 HO( 13 CH 2 O) n H D 2 O D 2 > HD > H 2 ; 13 CO 2 [(Ru(p-cymene)) 2 µ-h(d 13 CO 2 )µ-cl] + 8 a gaseous phase analysis by MS. b Major ruthenium species detected by NMR experiments and ESI-MS analysis of the liquid phase, for details and other species see SI. c HDO (mixture of H 2 O:D 2 O (1:1). d performed under argon enriched atmosphere for enhanced sensitivity to oxygen. e D 2 O formation was assigned by 2 HNMR of the liquid phase; n. a. = not analysed.

Supplementary Table 2: NMR spectroscopy details of 3: Chemical shifts (δ ppm), coupling constants (Hz) and relevant correlations. Carbon No. a δ C (ppm) δ H (ppm) H,H NOE correlations H,C l.r. couplings 3 J HH 1 176,0 (d) 6,80 1,20; -7,08 H -7,08-2 104,76 (s) - - H 5,82; 6,22; 6,42; 5,26; 2,68; 1,20-3 99,31 (s) - - H 5,82; 6,22; 6,42; 5,26; 2,05-4 85,7 (d) 5,82 6,22; 2,68; 1,20 H 6,42; 6,15; 2,05; -7,08. C 104,76; 99,31; 84,54; 80,97; 31,35 6,25 Hz 5 84,54 (d) 6,22 5,82; 2,05 H 5,82; 5,26; 2,05; -7,08. C 104,76; 99,31; 85,7; 77,92; 18,8 6,25 Hz 6 80,97 (d) 6,42 5,26; 2,68; 1,20; -7,08 H 5,82; 5,26; 2,68. C 104,76; 99,31; 85,7; 77,92; 31,35 6,10 Hz 7 77,92 (d) 5,26 6,42; 2,05; - 7,08 H 6,42; 6,22; 2,05. C 104,76; 99,31; 84,54; 80,97; 18,8 6,10 Hz 8 31,35 (d) 2,68 6,42; 5,82; 1,20; -7,08 H 6,42; 5,82; 1,20. C 104,76; 85,7; 80,97; 21,24 7,20 Hz 9 21,24 (q) 1,20 6,42; 5,82; 2,68; -7,08 H 2,68; 1,20. C 104,76; 31,35; 21,24 7,20 Hz 10 18,8 (q) 2,05 6,22; 5,26; - 7,08 - - -7,08 6,80; 6,42; 5,26; 2,68; 2,05; 1,20 H 6,22; 5,26. C 99,31; 84,54; 77,92 - C 176,0; 85,7; 84,54 - a) Numbering refers to Supplementary Fig. 6-7. Spectra were recorded at 298 K.

Supplementary Table 3: NMR spectroscopy details of 3-BF 4 : Chemical shifts (δ ppm), coupling constants (Hz) and relevant correlations. No. a H (J in Hz) C COSY HMBC NOESY HOESY 1 6.51 (d, 5.9) 80.9 2, 5 2, 3, 5, 6, 7 2, 7, 8, 12 BF 4 - (-152,0) 2 5.44 (d, 5.9) 78.8 1, 4, 10 1, 3, 4, 6, 10 1, 10 BF 4 - (-152,0) 3 97.8 4 6.17 (d, 6.1) 84.3 5, 2, 10 2, 3, 5, 6, 10 5, 10 5 5.79 (d, 6.0) 86.2 4, 1 1, 3, 4, 6, 7 4, 7, 9 6 104.6 7 2.70 (hept, 6.9) 31.6 8, 9 1, 5, 6, 8, 9 1, 5, 8, 9 8 1.31 (d, 6.9) 21.8 9 1.30 (d, 6.9) 22.7 7 6, 7 1, 5, 7 10 2.12 (s) 19.2 2, 4 2, 3, 4 2, 4, 12 BF - 4 (-152,0) 11 6.83 (d, 0.8) 174.9 9 12-7.26 (s) 4, 5, 11 1, 8 a) Numbering refers to Supplementary Fig. 6-7. Spectra were recorded at 298 K.

Supplementary References [1] Biro, L., Farkas, E. & Buglyo, P. Hydrolytic behaviour and chloride ion binding capability of [Ru(eta(6)-p-cym)(H2O)(3)](2+): a solution equilibrium study. Dalton T 41, 285-291, (2012).

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