Functional Modeling of Cobalamine-Independent Methionine Synthase with Pyrazolylborate−Zinc−Thiolate Complexes

A series of new pyrazolylborate−zinc−thiolate complexes TpPh,MeZn−SR and TpMe,MeZn−SR, including two homocysteine derivatives, were prepared and structurally characterized. Their reactions with methyl iodide in nonpolar media resulted in the formation of the thioethers MeSR, including two methionine derivatives, and TpR‘,MeZn−I in all cases. Methylation of the thiolates could also be achieved with dimethyl sulfate and trimethylsulfonium iodide but not with trimethyl phosphate or N-methylpyridinium salts. The accumulated evidence indicates that the methylation occurs intramolecularly, i.e., at the zinc-bound thiolates: (i) The reactions occur readily in nonpolar media. (ii) Thiolate exchange at TpPh,MeZn−SR with [PPN]SR‘ is slower than thiolate alkylation. (iii) The methylation of TpPh,MeZn−SBn with MeI is a clean second-order reaction with k‘ ‘ = 1.75 × 10-2 M-1 s-1 at 300 K.