A series of new pyrazolylborate-zinc-thiolate complexes Tp(Ph,Me)Zn-SR and Tp(Me,Me)Zn-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 Tp(R',Me)Zn-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 Tp(Ph,Me)Zn-SR with [PPN]SR' is slower than thiolate alkylation. (iii) The methylation of Tp(Ph,Me)Zn-SBn with MeI is a clean second-order reaction with k'' = 1.75 x 10(-2) M(-1) s(-1) at 300 K.
Four new hydrosulfide complexes Tp*Zn-SH of substituted pyrazolylborate ligands (Tp*) were prepared by reactions of Tp*Zn-OH with H(2)S, and three of them were structurally characterized. Unlike the Tp*Zn-OH complexes they do not react with esters, phosphates, or CO(2), e.g. for thiolytic cleavage reactions. They also cannot be deprotonated, as various bases induce precipitation of ZnS and release of anionic Tp*. Acidic organic X-OH compounds (carboxylic acids, trinitrophenol, hexafluoroacetylacetone) replace the SH groups with formation of Tp*Zn-OX. Thiols undergo an entropy-driven SH substitution to yield the Tp*Zn-SR complexes. Like the Tp*Zn-SR complexes the Tp*Zn-SH complexes are quite reactive toward alkylation with methyl iodide, yielding Tp*Zn-I and CH(3)SH. The kinetic investigation of the methylation of Tp(Ph,Me)Zn-SH has shown it to be a clean second-order reaction, thereby indicating that the SH group is alkylated in the zinc-bound state.
The biologically relevant alkylations of the thiolate ligands in tripod zinc thiolates by methyl iodide were studied kinetically. Five tripod ligands of the pyrazolyl/thioimidazolyl borate type were employed, offering N3, N2S, NS2, and S3 donor sets. For each of them, the ethyl-, benzyl-, phenyl-, and p-nitrophenylthiolate zinc complexes were investigated, yielding a total of 20 second-order rate constants. The comparison of these rate constants shows three effects: (1) the electronic effect among the thiolates, i.e., the ethanethiolates react about 3 orders of magnitude faster than the p-nitrophenylthiolates; (2) the steric effect among the pyrazolylborates, i.e., the phenyl-substituted ones react about 2 orders of magnitude faster than the tert-butyl-substituted ones; and (3) the strong acceleration by the sulfur donors in the tripods, reaching 4 orders of magnitude between the reaction times of the (N3)Zn-SR and (S3)Zn-SR complexes.
Pyrazolylborate-zinc-thiolate complexes react under mild conditions with methyl iodide, dimethylsulfate and trimethylsulfonium iodide, liberating the corresponding methyl thioethers; the driving force for these reactions lies in the high nucleophilicity of the zinc-bound thiolates and the low donor quality of thioethers toward zinc.
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