The catalytic networks of methylotrophic organisms, featuring redoxe nzymes for the activation of onecarbon moieties, can serve as great inspirationi nt he development of novel homogeneously catalyzed pathways for the interconversion of C 1 moleculesa tambient conditions. An imidazolium-tagged arene-ruthenium complex was identified as an effective functional mimico ft he bacterial formaldehyde dismutase,w hich providesan ew and highly selectiver oute for the conversion of formaldehyde to methanol in absence of any externalr educing agents. Moreover,s econdary amines are reductively methylated by the organometallic dismutase mimic in aredox self-sufficient mannerw ith formaldehyde acting both as carbon source and reducing agent.Methanola nd formaldehyde are key platform chemicals that are industriallyf ormed from syngaso nam egaton scale. [1][2][3] Currently,t hese reactionsa re carriedo ut at high temperatures and pressures over variousd ifferent heterogeneous catalysts. [4,5] Milder reaction conditions for the conversion of onecarbon entities have been achieved using well-definedmolecular metal catalysts. Therein, the most successful examplesc ommonly focussed on highly oxidized starting materials, such as carbon dioxide and formic acid. In addition to well-developed CO 2 to formater eduction protocols, [6][7][8][9][10][11] both multi-metallic approaches [12] and single-site catalysts ystems [13][14][15][16][17] have emerged en route to the homogeneously catalyzed methanol synthesis from CO 2 in the past five years.M oreover,t he methanol productionw as attempted by catalytic disproportionation of formic acid. Fighting against the favorable formate decomposition, [18] in 2014 ar uthenium-triphos complex was reported to generate MeOH in up to 50 %y ield along with at least two equivalents of CO 2 . [19] In nature,f ormaldehyde plays am uch more pronounced role within the familyo fC 1 molecules. Basedo na ne volutionary conserved detoxification mechanism, various methanol-tolerant or even methanol-feeding microorganisms have developed ab iocatalytic machinery to deal with,a nd benefit from formalin. In addition to the capability to include formaldehyde into the biosyntheticc arbon fixationb yt he ribulose monophosphate pathway, [20,21] methylotrophs exploit formalin, rather than methanol, as as ource of reduction equivalents. Therein, the preactivation of CH 2 Ob yt he formation of hemithioacetal conjugates with either cofactors (mycothiol or glutathione) [22,23] or protein-bound mercaptanes [24] allows for at ransferh ydrogenationt oN AD + ,i nw hich NADH is liberated to serve as biological reductant( Scheme1,t op left). Inspiredb yt his mode of action,w er ecently reported on ab iomimetic ruthenium-based H 2 release system using methanediol as simple tetrahedral formaldehyde conjugate analogue and hydrogena sa biotic NADH equivalent (Scheme 1, bottom left). [25] Ag reat number of C 1 -feeding bacterial strains,f or example Pseudomonas putida, Staphylococcus aureus,o rMycobacterium Scheme1.a) The prima...