The use of methanol as a C1 building block

Bhaskar Paul, Sabuj Kundu

Published: 2024-04-25 DOI: 10.1038/s41596-024-00978-0

Extended

Extended Data Fig. 1 Methanol distillation.

a , Full setup for methanol distillation from magnesium cake. b , Correct storage of distilled solvent in a round-bottom flask with a Suba seal under N 2 atmosphere. c , Argon inlet to solvent flask during use. After each use of distilled methanol, purge it with argon and handle the distilled solvent very carefully to prevent contamination with moisture. For the long-term use of distilled methanol, store it over 4-Å activated molecular sieves.

Extended Data Fig. 2 Ace pressure tubes.

a–c , Different types of pressure tube (2.5, 4 and 9 mL) used in the protocol. d , Cap and front seal. e , Front seal on the cap. f , PTFE tape. g , Front seal and thread on the cap cover by PTFE. Here, PTFE tape is used to avoid any leakage of solvent during the reaction at high temperature and to increase the lifespan of the front seal (O-ring) by avoiding direct contact of the O-ring with hot solvent during the experiment.

Extended Data Fig. 3 Experimental setup for the synthesis of ligand and images of dried reagent and ligand.

a , Detailed setup for the syntheses of NNN-OMe ( L1 ) and NNN-Me ( L3 ) ligands. b , Image of 2-bromo-1,10-phenanthroline. c , Image of ligand NNN-Me ( L3 ).

Extended Data Fig. 4 Ruthenium(II) precursors.

a , Tris(triphenylphosphine)ruthenium (II) dichloride (RuCl 2 (PPh 3 ) 3 ). b , Dichloro ( p -cymene) ruthenium (II) dimer ([RuCl 2 ( p -cymene)] 2 ).

Extended Data Fig. 5 Experimental setup for the synthesis of ruthenium (II) complexes and images of selected Ru (II) complexes.

a , Detailed setup for the syntheses of Ru-1 and Ru-2. b , Image of [RuCl(phenpy-OMe)(CH 3 CN) 2 ]Cl (Ru-1). c , Image of trans -RuCl(phenpyMe)(PPh 3 ) 2 PF 6 (Ru-3).

Extended Data Fig. 6 Selected substrates and products.

a–d , Substrates: nitrobenzene ( a ), benzonitrile ( b ), acetophenone ( c ) and benzamide ( d ). e–h , Products: N -methyl aniline ( e ), N , N -dimethyl benzylamine ( f ), 2-methyl-1-phenylpropan-1-one ( g ) and N -methyl benzamide ( h ).

Extended Data Fig. 7 Experimental setup for the synthesis of trans -RuCl(phenpyMe)(PPh 3 ) 2 PF 6 (Ru-3).

a , Reaction flask with magnetic stir bar. b , Full setup, during reflux. c , Reaction mixture at the end.

Extended Data Fig. 8 Experimental setup for the synthesis of NNN-OH ( L2 ) ligand.

Synthesis of L2 ligand from ligand L1 and aqueous HBr.

Extended Data Fig. 9 Ligand and cobalt precursors.

a , Tris[2-(diphenylphosphino)ethyl]phosphine (PP 3 ). b , Cobalt(II) bromide (CoBr 2 ). c , Cobalt(II) nitrate hexahydrate (Co(NO 3 ) 2 · 6 H 2 O).

Extended Data Fig. 10 Catalytic experimental setup with different types of pressure tubes.

a , c and e , Pressure tube with all reagents before adding solvent. b , d and f , Full experimental setup with 2.5-, 4- and 9-mL pressure tube, respectively.

Supplementary information

Supplementary Information

Supplementary Methods, Box 1, References and Figs. 1–6

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References

Introduction
Materials
Procedures
Troubleshooting
Timing
Anticipated results
Acknowledgements
Extended Data Fig. 1 Methanol distillation.
Extended Data Fig. 2 Ace pressure tubes.
Extended Data Fig. 3 Experimental setup for the synthesis of ligand and images of dried reagent and ligand.
Extended Data Fig. 4 Ruthenium(II) precursors.
Extended Data Fig. 5 Experimental setup for the synthesis of ruthenium (II) complexes and images of selected Ru (II) complexes.
Extended Data Fig. 6 Selected substrates and products.
Extended Data Fig. 7 Experimental setup for the synthesis of trans-RuCl(phenpyMe)(PPh3)2PF6 (Ru-3).
Extended Data Fig. 8 Experimental setup for the synthesis of NNN-OH (L2) ligand.
Extended Data Fig. 9 Ligand and cobalt precursors.
Extended Data Fig. 10 Catalytic experimental setup with different types of pressure tubes.

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