Synthesis of acetic acid from methanol alone by homogeneous metal complex catalyst. Part 4. In-situ formation of catalyst species and halogen effect in the RuCl3·3H2O–SnX2 (X=F, Cl, Br, I) composite system

Highly selective formation of methyl acetate has been found possible from methanol alone using the catalyst generated in situ from RuCl₃·3H₂O and SnCl₂ as well as SnX₂ (X=F, Br, I). The reaction did not occur in the absence of SnCl₂ added and the optimum Sn]/Ru] ratio appeared at about 16. The halogen effect showed the order of SnF₂>SnCl₂>SnBr₂>SnI₂, which indicates the importance of cationic character of Ru(II) center to facilitate its electrophilic interaction with β-hydrogen of Ru–OCH₃ intermediate in the rate-limiting dehydrogenation step.