Hydrosilane σ-Adduct Intermediates in an Adaptive Zinc-Catalyzed Cross-dehydrocoupling of Si-H and O-H Bonds.

ABSTRACT: Three-coordinate ^Ph BOX Me 2 ZnR (^Ph BOX Me 2 =phenyl-(4,4-dimethyl-oxazolinato; R=Me: 2 a, Et: 2 b) catalyzes the dehydrocoupling of primary or secondary silanes and alcohols to give silyl ethers and hydrogen, with high turnover numbers (TON; up to 10⁷ ) under solvent-free conditions. Primary and secondary silanes react with small, medium, and large alcohols to give various degrees of substitution, from mono- to tri-alkoxylation, whereas tri-substituted silanes do not react with MeOH under these conditions. The effect of coordinative unsaturation on the behavior of the Zn catalyst is revealed through a dramatic variation of both rate law and experimental rate constants, which depend on the concentrations of both the alcohol and hydrosilane reacta

SUBMITTER: Patnaik S 

PROVIDER: S-EPMC8362191 | biostudies-literature | 2021 Jul

REPOSITORIES: biostudies-literature