A series of heterogenized Rh complex catalysts for the carbonylation of MeOH were synthesized by the reaction of Rh2(CO)4Cl2 with linear and cross-linked copolymers of 2-vinylpyridine and Me vinyl ketone. The active centers of these catalysts consist of (1) a cis-Rh(CO)2 moiety coordinated with the borderline base pyridine N and the adjacent hard base keto O to form N甊h and O甊h coordination bond, resp., and (2) the said moiety coordinated with 2 adjacent pyridine N's to form 2 N甊h bonds. The former plays a more active role than the latter in catalysis. These catalysts are thermally stable. With MeI as promoter, MeOH in AcOH could be carbonylated to AcOH and Ac2O simultaneously as final products with a turnover rate at 104 mol of MeOH converted/mol Rh/h.

Key words: PYRIDINE P, CATALYSIS, CATALYST, METHANOL, COPOLYMERS, STRUCTURE AND PROPERTY CORRELATION, ACETIC ACID, CARBONYLATION, CROSSLINKING, RHODIUM COMPLEX